Polyamide, polyamide composition, and method for producing polyamide

ABSTRACT

The present invention relates to a polyamide obtainable by polymerizing an (a) dicarboxylic acid comprising at least 50 mol % of an alicyclic dicarboxylic acid and a (b) diamine comprising at least 50 mol % of a diamine having a substituent branched from a main chain.

CLAIM FOR PRIORITY

This application is a continuation of U.S. application Ser. No.12/921,815, which is a National Phase of PCT/JP2009/054693 filed Mar.11, 2009, and claims the priority benefit of Japanese Applications No.2008-062811, filed Mar. 12, 2008, No. 2008-075926, filed Mar. 24, 2008,and No. 2008-264182, filed Oct. 10, 2008, the contents of each of whichare expressly incorporated by reference in their entireties.

TECHNICAL FIELD

The present invention relates to a polyamide, a polyamide composition,and a method for producing polyamide.

BACKGROUND ART

Polyamides represented by polyamide 6 and polyamide 66 (hereinafter,sometimes referred to as “PA6” and “PA66”, respectively) and the likehave excellent molding processability, mechanical properties, orchemical resistance. Therefore, polyamides are widely used as a materialfor various parts, such as for automobiles, electric and electronicparts, industrial materials, and daily and household articles.

In the automotive industry, as an environmental measure, there is a needto lighten the weight of the automobile body by using a metal substitutein order to reduce exhaust gases. To respond to this need, polyamidesare being increasingly used for exterior materials, interior materialsand the like. Further, the level of the properties required forpolyamide materials, such as heat resistance, strength, and appearance,is dramatically increasing. However, the temperature in the engine roomis also tending to increase, so that the need to increase the heatresistance of polyamide materials is growing stronger.

Further, in the electric and electronics industry, such as householdappliances, there is a need for increased heat resistance for polyamidematerials which are capable of withstanding the increased melting pointof the solder required for lead-free solder for using surface mountingtechnology (SMT).

PA6 and PA66 polyamides are unable to satisfy these requirements interms of heat resistance, since their melting point is low.

To resolve the above-described problems with conventional polyamidessuch as PA6 and PA66, a high-melting-point polyamide has been proposed.Specifically, a polyamide formed from terephthalic acid andhexamethylenediamine (hereinafter, sometimes referred to as “PA6T”) hasbeen proposed.

However, PA6T is a high-melting-point polyamide having a melting pointof about 370° C. Therefore, even if a molded product is obtained by meltkneading, pyrolysis of the polyamide is severe, which makes it difficultto obtain a molded product having sufficient properties.

To resolve the above-described problem with PA6T, a high-melting-pointsemi-aromatic polyamide (hereinafter, sometimes referred to as “6T-basedcopolyamide”) and the like comprising terephthalic acid and ahexamethylenediamine as main components has been proposed. Thishigh-melting-point semi-aromatic polyamide has a melting point loweredto about 220 to 340° C. by copolymerizing an aliphatic polyamide, suchas PA6 and PA66, and the amorphous aromatic polyamide formed fromhexamethylendiamine and isophthalic acid (hereinafter, sometimesreferred to as “PA6I) and the like with PA6T.

As a 6T-based copolyamide, Patent Document 1 describes an aromaticpolyamide (hereinafter, sometimes referred to as “PA6T/2 MPDT) which isformed from an aromatic dicarboxylic acid and an aliphatic diamine, inwhich the aliphatic diamine is a mixture of hexamethylenediamine and2-methylpentamethylenediamine.

Further, in contrast to an semi-aromatic polyamide formed from anaromatic dicarboxylic acid and an aliphatic diamine, ahigh-melting-point aliphatic polyamide (hereinafter, sometimes referredto as “PA46”) formed from adipic acid and tetramethylenediamine, and analicyclic polyamide formed from an alicyclic dicarboxylic acid and analiphatic diamine, and the like have been proposed.

Patent Documents 2 and 3 describe a semi-alicyclic polyamide(hereinafter, sometimes referred to as “PA6C copolyamide”) which isformed from an alicyclic polyamide (hereinafter, sometimes referred toas “PA6C”) formed from 1,4-cyclohexanedicarboxylic acid andhexamethylenediamine, and another polyamide.

Patent Document 2 describes that electric and electronic parts formedfrom a semi-alicyclic polyamide blended with 1 to 40% of1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid unit haveimproved solder heat resistance. Patent Document 3 describes that forautomobile components, fluidity, toughness and the like are excellent.

In addition, Patent Document 4 describes that a polyamide formed from adicarboxylic acid unit comprising 1,4-cyclohexanedicarboxylic acid and adiamine unit comprising 2-methyl-1,8-octanediamine has excellent lightfastness, toughness, moldability, low weight, heat resistance and thelike. Moreover, as a production method for such a polyamide, PatentDocument 4 describes that a polyamide having a melting point of 311° C.is produced by reacting 1,4-cyclohexanedicarboxylic acid and1,9-nonanediamine at 230° C. or less to produce a prepolymer, which isthen subjected to solid phase polymerization at 230° C.

Further, Patent Document 5 describes that a polyamide using1,4-cyclohexanedicarboxylic acid having a trans/cis ratio of from 50/50to 97/3 as a raw material has excellent heat resistance, low waterabsorbance, and light fastness.

-   Patent Document 1: National Publication of International Patent    Application No. 1994 (Hei 6)-503590-   Patent Document 2: National Publication of International Patent    Application No. 1999 (Hei 11)-512476-   Patent Document 3: National Publication of International Patent    Application No. 2001-514695-   Patent Document 4: Japanese Patent Laid-Open No. 9-12868-   Patent Document 5: WO 2002/048239 pamphlet

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

Although 6T-based copolyamides certainly have properties such as lowwater absorbance, high heat resistance, and high chemical resistance,their fluidity is low, and their moldability and the surface appearanceof the molded product is insufficient. In addition, their toughness andlight fastness is poor. Consequently, there is a need for improvementfor applications which require a good molded product appearance, such asan exterior component, or which are exposed to sunlight and the like.Moreover, 6T-based copolyamides have a large specific weight, so thatthere is a need for improvement in terms of reducing weight as well.

Although the PA6/2 MPDt described in Patent Document 1 can partiallyimprove on the problems of conventional PA6T copolymers, the level ofimprovement in terms of fluidity, moldability, toughness molded productsurface appearance, and light fastness is insufficient.

Although PA46 has good heat resistance and moldability, PA46 suffersfrom the problems of high water absorbance. Further, the dimensionalchange and deterioration in mechanical properties due to waterabsorbance is very large. Thus, in some cases PA46 cannot satisfy thedimensional change requirement required for automobile applications.

The PA6C copolyamide described in Patent Documents 2 and 3 also suffersfrom problems such as having a high water absorbance and insufficientfluidity.

For the polyamides described in Patent Documents 4 and 5 too, theimprovement in terms of toughness, rigidity, and fluidity isinsufficient.

It is an object of the present invention to provide a polyamide having ahigh melting point, which has excellent heat resistance, fluidity,toughness, low water absorbance, and rigidity.

Means for Solving the Problems

As a result of continued intensive investigations into resolving theabove-described problems, the present inventors discovered that apolyamide obtained by polymerizing, as the main constituent components,an alicyclic dicarboxylic acid and a diamine having a substituentbranched from a main chain can resolve the above-described problems,thereby arriving at the present invention.

More specifically, the present invention is as follows.

(1) A polyamide obtainable by polymerizing (a) dicarboxylic acidcomprising at least 50 mol % of an alicyclic dicarboxylic acid and (b)diamine comprising at least 50 mol % of a diamine having a substituentbranched from a main chain.

(2) The polyamide according to (1), wherein the diamine having thesubstituent branched from the main chain is2-methylpentamethylenediamine.

(3) The polyamide according to (1) or (2), wherein the alicyclicdicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.

(4) The polyamide according to any one of (1) to (3), wherein thedicarboxylic acid further comprises an aliphatic dicarboxylic acidhaving 10 or more carbon atoms.

(5) The polyamide according to any one of (1) to (4), which isobtainable by further copolymerizing with a (c) lactam and/oraminocarboxylic acid.

(6) The polyamide according to any one of (1) to (5), which has amelting point of from 270 to 350° C.

(7) The polyamide according to any one of (1) to (6), which has a transisomer ratio of from 50 to 85%.

(8) The polyamide according to any one of (1) to (7), which has a bvalue of 0 or less.

(9) A polyamide composition comprising:

(A) a polyamide according to any one of (1) to (8); and

(B) an inorganic filler.

(10) A polyamide composition comprising:

(A) a polyamide according to any one of (1) to (8); and

(C) a copper compound and a metal halide.

(11) A polyamide composition comprising:

a polyamide according to any one of (1) to (8); and

(D) a halogen-based flame retardant.

(12) A polyamide composition comprising:

(A) a polyamide according to any one of (1) to (8); and

(E) a phosphinate and/or diphosphinate.

(13) A polyamide composition comprising:

(A) a polyamide according to any one of (1) to (8); and

(F) a stabilizer.

(14) An automobile component, comprising a polyamide compositionaccording to any one of (9) to (13).

(15) The automobile component according to (14), which is an automobileair intake system component or an automobile cooling system component.

(16) A method for producing a polyamide, comprising a step ofpolymerizing an (a) dicarboxylic acid comprising at least 50 mol % of analicyclic dicarboxylic acid and a (b) diamine comprising at least 50 mol% of an aliphatic diamine having a substituent branched from a mainchain.(17) The method for producing the polyamide according to (16), whereinthe polymerization is carried out while maintaining a trans isomer ratioat from 50 to 80%.(18) A polyamide obtainable by the method of (16) or (17).

Advantages of the Invention

According to the present invention, a high-melting-point polyamide canbe provided, which has excellent heat resistance, fluidity, toughness,low water absorbance, and rigidity.

BEST MODE FOR CARRYING OUT THE INVENTION

A best mode for carrying out the present invention (hereinafter referredto as “the present embodiment”) is described below in more detail.However, the present invention is not limited to the followingembodiment, and can be variously modified within the scope of the intentof the invention.

Polyamide

The polyamide according to the present embodiment is a polyamideobtained by polymerizing the following (a) and (b):

an (a) dicarboxylic acid comprising at least 50 mol % of an alicyclicdicarboxylic acid, and

a (b) diamine comprising at least 50 mol % of a diamine having asubstituent branched from a main chain.

In the present embodiment, “polyamide” means a polymer which has anamide (—NHCO—) bond in a main chain.

(a) Dicarboxylic acid

The (a) dicarboxylic acid used in the present embodiment comprises atleast 50 mol % of an alicyclic dicarboxylic acid.

By comprising at least 50 mol % of the alicyclic dicarboxylic acid asthe (a) dicarboxylic acid, the polyamide can be obtained whichsimultaneously satisfies heat resistance, fluidity, toughness, low waterabsorbance, rigidity and the like.

Examples of the (a-1) alicyclic dicarboxylic acid (also referred to ascycloaliphatic dicarboxylic acid) include alicyclic dicarboxylic acidshaving an alicyclic structure with 3 to 10 carbon atoms, and preferably5 to 10 carbon atoms, such as 1,4-cyclohexanedicarboxylic acid,1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid.The alicyclic dicarboxylic acid may optionally have a substituent.

In the present embodiment, examples of the substituent include an alkylgroup having 1 to 4 carbon atoms, such as a methyl group, an ethylgroup, a n-propyl group, an isopropyl group, a n-butyl group, anisobutyl group, and a tert-butyl group.

From perspectives such as heat resistance, fluidity, and rigidity,1,4-cyclohexanedicarboxylic acid is preferred as the alicyclicdicarboxylic acid.

As the alicyclic dicarboxylic acid, one kind may be used, or two or morekinds may be used in combination.

Alicyclic dicarboxylic acids have trans and cis geometric isomers.

The alicyclic dicarboxylic acid used as a raw material monomer may beeither a trans or a cis isomer. The alicyclic dicarboxylic acid may alsobe used as a mixture of trans and cis isomers in various ratios.

Since alicyclic dicarboxylic acids isomerize in a fixed ratio at hightemperatures, and the cis isomer has a higher water solubility than thetrans isomer in an equivalent amount of salt with a diamine, as the rawmaterial monomer, a trans isomer/cis isomer ratio is, based on molarratio, preferably 50/50 to 0/100, more preferably 40/60 to 10/90, andstill more preferably 35/65 to 15/85.

The alicyclic dicarboxylic acid trans isomer/cis isomer ratio (molarratio) can be determined by liquid chromatography (HPLC) or NMR.

Examples of an (a-2) dicarboxylic acid other than the alicyclicdicarboxylic acid in the (a) dicarboxylic acid used in the presentembodiment include aliphatic dicarboxylic acids and aromaticdicarboxylic acids.

Examples of the aliphatic dicarboxylic acid include straight-chain orbranched saturated aliphatic dicarboxylic acids having 3 to 20 carbonatoms, such as malonic acid, dimethylmalonic acid, succinic acid,2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid,2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, glutaric acid,2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid,dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid,octadecanedioic acid, eicosane diacid, and diglycolic acid.

Examples of the aromatic dicarboxylic acid include aromatic dicarboxylicacids, which are unsubstituted or substituted with various substituents,having 8 to 20 carbon atoms, such as terephthalic acid, isophthalicacid, naphthalene dicarboxylic acid, 2-chloroterephthalic acid,2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodiumsulfoisophthalic acid.

Examples of the various substituents include an alkyl group having 1 to6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkylgroup having 7 to 20 carbon atoms, a halogen group such as a chlorogroup or a bromo group, an alkylsilyl group having 3 to 10 carbon atoms,and a sulfonic acid group or salt thereof, such as a sodium salt.

As the dicarboxylic acid other than the alicyclic dicarboxylic acid,from perspectives such as heat resistance, fluidity, toughness, lowwater absorbance, and rigidity, an aliphatic dicarboxylic acid ispreferred, and more preferred is an aliphatic dicarboxylic acid having 6or more carbon atoms.

Of these, from perspectives such as heat resistance and low waterabsorbance, an aliphatic dicarboxylic acid having 10 or more carbonatoms is preferred.

Examples of the aliphatic dicarboxylic acids having 10 or more carbonatoms include sebacic acid, dodecanedioic acid, tetradecanedioic acid,hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid.

Of these, from perspectives such as heat resistance, sebacic acid anddodecanedioic acid are preferred.

As the dicarboxylic acid other than the alicyclic dicarboxylic acid, onekind may be used, or two or more kinds may be used in combination.

To the extent that the object of the present embodiment is not harmed,the (a) dicarboxylic acid may further include a trivalent or higherpolyvalent carboxylic acid, such as trimellitic acid, trimesic acid, andpyromellitic acid.

As the polyvalent carboxylic acid, one kind may be used, or two or morekinds may be used in combination.

A ratio of the (a-1) alicyclic dicarboxylic acid in the (a) dicarboxylicacid is at least 50 mol %. The ratio of the alicyclic dicarboxylic acidis 50 to 100 mol %, and preferably 60 to 100%. By setting the ratio ofthe alicyclic dicarboxylic acid to be at least 50 mol %, the polyamidecan be obtained which simultaneously satisfies heat resistance,fluidity, toughness, low water absorbance, rigidity and the like.

A ratio of the (a-2) dicarboxylic acid other than the alicyclicdicarboxylic acid in the (a) dicarboxylic acid is 0 to 50 mol %, andpreferably 0 to 40%.

It is preferred that the (a-1) alicyclic dicarboxylic acid is 50.0 to99.9 mol % and the (a-2) aliphatic dicarboxylic acid having 10 or morecarbon atoms is 0.1 to 50.0 mol %. It is more preferred that the (a-1)alicyclic dicarboxylic acid is 60.0 to 90.0 mol % and the (a-2)aliphatic dicarboxylic acid having 10 or more carbon atoms is 10.0 to40.0 mol %. It is still more preferred that the (a-1) alicyclicdicarboxylic acid is 70.0 to 85.0 mol % and the (a-2) aliphaticdicarboxylic acid having 10 or more carbon atoms is 15.0 to 30.0 mol %.

In the present embodiment, the (a) dicarboxylic acid is not limited tothe compounds described above as dicarboxylic acids. The dicarboxylicacid may be a compound equivalent to those described above.

Examples of compounds equivalent to those described above are notespecially limited, as long as such compound can have the samedicarboxylic acid structure as a dicarboxylic acid structure derivedfrom the above-described dicarboxylic acids. Examples thereof includeanhydrides and halides of the dicarboxylic acid.

(b) Diamine

The (b) diamine used in the present embodiment comprises at least 50 mol% of a diamine having a substituent branched from a main chain.

By comprising at least 50 mol % of the diamine having the substituentbranched from the main chain in the (b) diamine, the polyamide can beobtained which simultaneously satisfies fluidity, toughness, rigidityand the like.

Examples of the substituent branched from the main chain include analkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethylgroup, a n-propyl group, an isopropyl group, a n-butyl group, anisobutyl group, and a tert-butyl group.

Examples of the (b-1) diamine having the substituent branched from themain chain include branched saturated aliphatic diamines having 3 to 20carbon atoms, such as 2-methylpentamethylenediamine (also referred to as2-methyl-1,5-diaminopentane), 2,2,4-trimethylhexamethylenediamine,2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, and2,4-dimethyloctamethylenediamine.

From perspectives such as rigidity, the diamine having the substituentbranched from the main chain is preferably2-methylpentamethylenediamine.

As the diamine having the substituent branched from the main chain, onekind may be used, or two or more kinds may be used in combination.

Examples of a (b-2) diamine other than the diamine having thesubstituent branched from the main chain in the (b) diamine used in thepresent embodiment include aliphatic diamines, alicyclic diamines, andaromatic diamines.

Examples of the aliphatic diamines include straight-chain saturatedaliphatic diamines having 2 to 20 carbon atoms, such as ethylenediamine,propylenediamine, tetramethylenediamine, pentamethylenediamine,hexamethylenediamine, heptamethylenediamine, octamethylenediamine,nonamethylenediamine, decamethylenediamine, undecamethylenediamine,dodecamethylenediamine, and tridecamethylenediamine.

Examples of the alicyclic diamines (also referred to as cycloaliphaticdiamines) include 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and1,3-cyclopentanediamine.

Examples of aromatic diamines include meta-xylylenediamine.

From perspectives such as heat resistance, fluidity, toughness, lowwater absorbance, and rigidity, an aliphatic diamine and an alicyclicdiamine are preferred as the diamine other than the diamine having thesubstituent branched from the main chain. More preferred is astraight-chain saturated aliphatic diamine having 4 to 13 carbon atoms,still more preferred is a straight-chain saturated aliphatic diaminehaving 6 to 10 carbon atoms, and even still more preferred ishexamethylenediamine.

As the diamine other than the diamine having the substituent branchedfrom the main chain, one kind may be used, or two or more kinds may beused in combination.

To the extent that the object of the present embodiment is not harmed,the (b) diamine may further include a trivalent or higher polyvalentaliphatic amine, such as bishexamethylenetriamine.

As the polyvalent aliphatic amine, one kind may be used, or two or morekinds may be used in combination.

A ratio of the (b-1) diamine having the substituent branched from themain chain in the (b) diamine is at least 50 mol %. The ratio of thediamine having the substituent branched from the main chain is 50 to 100mol %, and preferably 60 to 100%. By setting the ratio of the diaminehaving the substituent branched from the main chain to be at least 50mol %, the polyamide can be obtained which has excellent fluidity,toughness, rigidity and the like.

A ratio of the (b-2) diamine other than the diamine having thesubstituent branched from the main chain in the (b) diamine is 0 to 50mol %, and preferably 0 to 40%.

An added amount of the (a) dicarboxylic acid is preferably about thesame molar amount as an added amount of the (b) diamine. Consideringescape out of the (b) diamine reaction system during the polymerizationreaction, based on an (a) dicarboxylic acid molar amount of 1.00, thetotal (b) diamine molar amount is preferably 0.90 to 1.20, morepreferably 0.95 to 1.10, and still more preferably 0.98 to 1.05.

(c) Lactam and/or Aminocarboxylic Acid

From the perspective of toughness, it is preferred to obtain thepolyamide according to the present embodiment by further copolymerizingwith a (c) lactam and/or aminocarboxylic acid.

The term “(c) lactam and/or aminocarboxylic acid” used in the presentembodiment means a lactam and/or aminocarboxylic acid capable ofpolycondensation.

The lactam and/or aminocarboxylic acid is preferably a lactam and/oraminocarboxylic acid having 4 to 14 carbon atoms, and more preferably alactam and/or aminocarboxylic acid having 6 to 12 carbon atoms.

Examples of the lactam include butyrolactam, pivalolactam,ε-caprolactam, caprylolactam, enantholactam, undecanonelactam, andlaurolactam (dodecanolactam).

Of these, from the perspective of toughness, ε-caprolactam, laurolactamand the like are preferred, and ε-caprolactam is more preferred.

Examples of the aminocarboxylic acid include ω-aminocarboxylic acid andα,ω-aminocarboxylic acid, which are compounds obtained by opening thering of the above-described lactams.

As the aminocarboxylic acid, a straight-chain or branched saturatedaliphatic carboxylic acid having 4 to 14 carbon atoms substituted at theω position with an amino group is preferred. Examples thereof include6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoicacid. Further examples of the aminocarboxylic acid includepara-aminomethylbenzoic acid.

As the lactam and/or aminocarboxylic acid, one kind may be used, or twoor more kinds may be used in combination.

An added amount of the (c) lactam and/or aminocarboxylic acid ispreferably 0 to 20 mol % based on a total molar amount of the respectivemonomers of (a), (b), and (c).

When polymerizing the polyamide from the (a) dicarboxylic acid and the(b) diamine, a known end-capping agent can be added for molecular weightregulation.

Examples of the end-capping agent include monocarboxylic acids,monoamines, acid anhydrides such as phthalic anhydride, monoisocyanates,monoacid halides, monoesters, and monoalcohols. From the perspective ofthermal stability of the polyamide, monocarboxylic acids and monoaminesare preferred.

As the end-capping agent, one kind may be used, or two or more kinds maybe used in combination.

Examples of monocarboxylic acids which can be used as the end-cappingagent are not especially limited, as long as the monocarboxylic acid isreactive with an amino group. Examples thereof include: aliphaticmonocarboxylic acids such as formic acid, acetic acid, propionic acid,butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid,tridecyl acid, myristic acid, pulmitic acid, stearic acid, pivalic acid,and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; and aromatic monocarboxylic acids such as benzoic acid,toluic acid, α-naphthalene carboxylic acid, β-naphthalene carboxylicacid, methylnaphthalene carboxylic acid, and phenylacetic acid.

As the monocarboxylic acid, one kind may be used, or two or more kindsmay be used in combination.

Examples of monoamines which can be used as the end-capping agent arenot especially limited, as long as the monoamine is reactive with acarboxyl group. Examples thereof include: aliphatic monoamines such asmethylamine, ethylamine, propylamine, butylamine, hexylamine,octylamine, decylamine, stearylamine, dimethylamine, diethylamine,dipropylamine, and dibutylamine; alicyclic monoamines such ascyclohexylamine and dicyclohexylamine; and aromatic monoamines such asaniline, toluidine, diphenylamine, and naphthylamine.

As the monoamine, one kind may be used, or two or more kinds may be usedin combination.

Preferred combinations of the (a) dicarboxylic acid and (b) diamineinclude, but are not limited to, (a-1) at least 50 mol % or more ofalicyclic dicarboxylic acid and (b-1) at least 50 mol % or more of2-methylpentamethylenediamine. More preferred is (a-1) at least 50 mol %or more of 1,4-cyclohexanedicarboxylic acid and (b-1) at least 50 mol %or more of 2-methylpentamethylenediamine.

By polymerizing these combinations as the polyamide components, ahigh-melting-point polyamide can be obtained which simultaneouslysatisfies heat resistance, fluidity, toughness, low water absorbance,and rigidity.

In the polyamide according to the present embodiment, the alicyclicdicarboxylic acid structure exists as cis and trans geometric isomers.

The trans isomer ratio of the alicyclic dicarboxylic acid structure inthe polyamide represents the ratio of trans isomers based on the wholealicyclic dicarboxylic acid in the polyamide. The trans isomer ratio ispreferably 50 to 85 mol %, more preferably 50 to 80 mol %, and stillmore preferably 60 to 80 mol %.

As the (a-1) alicyclic dicarboxylic acid, it is preferred to use analicyclic dicarboxylic acid having a trans/cis ratio (molar ratio) of50/50 to 0/100. However, as the polyamide obtained by polymerization ofthe (a) dicarboxylic acid and (b) diamine, the trans isomer ratio ispreferably 50 to 85 mol %.

By setting the trans isomer ratio in the above-described range, inaddition the characteristics of a high melting point and excellenttoughness and rigidity, the polyamide has qualities which simultaneouslysatisfy rigidity during heating due to a high glass transitiontemperature, fluidity, which is generally a quality that conflicts withheat resistance, a high crystallinity, and low water absorbance.

These characteristics of the polyamide are especially pronounced for apolyamide formed from the combination of (a) at least 50 mol % or moreof 1,4-cyclohexanedicarboxylic acid and (b) at least 50 mol % or more of2-methylpentamethylenediamine, and which has a trans isomer ratio offrom 50 to 85 mol %.

In the present embodiment, the trans isomer ratio can be measured by themethod described in the below examples.

A method for producing the polyamide according to the present embodimentis not especially limited, as long as it is a polyamide productionmethod which comprises a step of polymerizing an (a) dicarboxylic acidcomprising at least 50 mol % of an alicyclic dicarboxylic acid and a (b)diamine comprising at least 50 mol % of a diamine having a substituentbranched from a main chain.

It is preferred that a method for producing the polyamide furthercomprises a step of increasing the degree of polymerization of thepolyamide.

As illustrated by the following production method examples, there arevarious methods for producing the polyamide.

1) Heating an aqueous solution or an aqueous suspension of thedicarboxylic acid and the diamine, or an aqueous solution or an aqueoussuspension of a mixture of the dicarboxylic acid, the diamine salt, andanother component (hereinafter, abbreviated as “that mixture” in thefollowing paragraphs), and polymerizing while maintaining the melt state(hereinafter, sometimes abbreviated as “hot melt polymerization”).2) Increasing the degree of polymerization while maintaining a solidstate at a temperature at or below the melting point of the polyamideobtained by hot melt polymerization (hereinafter, sometimes abbreviatedas “hot melt polymerization/solid phase polymerization”)3) Heating an aqueous solution or an aqueous suspension of thedicarboxylic acid and the diamine or a mixture thereof, and increasingthe degree of polymerization by further re-melting the precipitatedprepolymer with an extruder such as a kneader (hereinafter, sometimesabbreviated as “prepolymer/extrusion polymerization”).4) Heating an aqueous solution or an aqueous suspension of thedicarboxylic acid and the diamine or a mixture thereof, and increasingthe degree of polymerization while maintaining the precipitatedprepolymer in a solid state at a temperature at or below the meltingpoint of the polyamide (hereinafter, sometimes abbreviated as“prepolymer/solid phase polymerization”).5) Polymerizing the dicarboxylic acid and the diamine, or a mixturethereof, while maintaining a solid state (hereinafter, sometimesabbreviated as “solid phase polymerization”).6) A “solution method” in which polymerization is carried out using adicarboxylic acid halide equivalent to the dicarboxylic acid and thediamine.

In the polyamide production method, it is preferred to carry outpolymerization while maintaining the trans isomer ratio of the alicyclicdicarboxylic acid at from 50 to 85%. From the perspective of fluidity ofthe polyamide, it is more preferred to carry out polymerization whilemaintaining at from 50 to 80%

By maintaining the trans isomer ratio in the above-described range,especially at 80% or less, a high-melting-point polyamide havingexcellent color tone and tensile elongation can be obtained.

In the polyamide production method, to increase the melting point of thepolyamide by increasing the degree of polymerization, it is necessary toincrease the heating temperature and/or lengthen the heating time.However, in such a case, the polyamide may color due to the heating andthe tensile elongation may deteriorate due to thermal degradation.Further, a rate of increase of the molecular weight may alsodramatically deteriorate.

To prevent deterioration in the coloration of the polyamide anddeterioration in tensile elongation due to thermal degradation, thepolymerization is preferably carried out while maintaining the transisomer ratio of the alicyclic dicarboxylic acid at 80% or less.

Since it is easy to maintain the trans isomer ratio at 80% or less, andsince the obtained polyamide has excellent color tone, it is preferredto produce the polyamide by 1) hot melt polymerization and 2) hot meltpolymerization/solid phase polymerization.

In the polyamide production method, the polymerization mode may beeither a batch method or a continuous method.

The polymerization apparatus is not especially limited. Examples of thepolymerization apparatus include known apparatuses, such as an autoclavetype reactor, a tumbler type reactor, and an extruder type reactor suchas a kneader.

The polyamide production method is not especially limited. For example,the polyamide can be produced by the batch hot melt polymerizationmethod described below.

Batch hot melt polymerization may be carried out by, for example, withwater as a solvent, concentrating an approximately 40 to 60 mass %solution containing the polyamide components ((a) dicarboxylic acid, (b)diamine, and optionally (c) lactam and/or aminocarboxylic acid) in aconcentration tank operated at a temperature of 110 to 180° C. and apressure of about 0.035 to 0.6 MPa (gauge pressure) to about 65 to 90mass % to obtain a concentrated solution. Then, this concentratedsolution is transferred to an autoclave, and heating is continued untilthe pressure in the vessel reaches 1.5 to 5.0 MPa (gauge pressure).Subsequently, the pressure is kept at 1.5 to 5.0 MPa (gauge pressure)while extracting water and/or the gas component. When the temperaturereaches about 250 to 350° C., the pressure is reduced to atmosphericpressure (gauge pressure of 0 MPa). After reducing the pressure toatmospheric pressure, the water produced as a byproduct can beeffectively removed by reducing the pressure as necessary. Then, thepressure is increased with an inert gas such as nitrogen, and apolyamide melt product is extruded as a strand. This strand is cooledand cut to obtain a pellet.

The polyamide production method is not especially limited. For example,the polyamide can be produced by the continuous hot melt polymerizationmethod described below.

Continuous hot melt polymerization can be carried out by, for example,with water as a solvent, pre-heating an approximately 40 to 60 mass %solution containing the polyamide components in the vessel of apreliminary apparatus to a temperature of 40 to 100° C. Then, thepre-heated solution is transferred to a concentration tank/reactor, andconcentrated to about 70 to 90% at a pressure of about 0.1 to 0.5 MPa(gauge pressure) and a temperature of about 200 to 270° C. to obtain aconcentrated solution. This concentrated solution is discharged into aflusher having a temperature maintained at about 200 to 350° C.Subsequently, the pressure is reduced to atmospheric pressure (gaugepressure of 0 MPa). After reducing the pressure to atmospheric pressure,the pressure is reduced as necessary. Then, a polyamide melt product isextruded as a strand. This strand is cooled and cut to obtain a pellet.

A molecular weight of the polyamide in the present embodiment isdetermined by using relative viscosity ηr at 25° C. as an index.

From the perspectives of mechanical properties such as toughness andrigidity, and of moldability, the polyamide according to the presentembodiment preferably has a molecular weight at a relative viscosity ηrat 25° C. at a 1% concentration in 98% sulfuric acid as measured basedon JIS-K6810 of 1.5 to 7.0, more preferably 1.7 to 6.0, and still morepreferably 1.9 to 5.5.

Measurement of the relative viscosity at 25° C. can be carried out basedon JIS-K6810 as described in the below examples.

From the perspective of heat resistance, the polyamide according to thepresent embodiment preferably has a melting point, referred to as Tm2,of from 270 to 350° C. The melting point Tm2 is preferably 270° C. ormore, more preferably 275° C. or more, and still more preferably 280° C.or more. Further, the melting point Tm2 is preferably 350° C. or less,more preferably 340° C. or less, and still more preferably 330° C. orless.

By setting the polyamide melting point Tm2 to be 270° C. or more, apolyamide having excellent heat resistance can be obtained. By settingthe polyamide melting point Tm2 to be 350° C. or less, pyrolysis of thepolyamide during melt processing such as extrusion and molding can besuppressed.

From the perspective of heat resistance, a heat of fusion ΔH of thepolyamide according to the present embodiment is preferably 10 or moreJ/g, more preferably 14 or more J/g, still more preferably 18 or moreJ/g, and even still more preferably 20 or more J/g.

Measurement of the melting point (Tm1 or Tm2) and the heat of fusion ΔHof the polyamide according to the present embodiment can be carried outbased on JIS-K7121 as described in the below examples.

Examples of the melting point and heat of fusion measurement apparatusinclude the Diamond-DSC, manufactured by PERKIN-ELMER Inc.

The polyamide according to the present embodiment preferably has a glasstransition temperature Tg of from 90 to 170° C. The glass transitiontemperature is preferably 90° C. or more, more preferably 100° C. ormore, and still more preferably 110° C. or more. Further, the glasstransition temperature is preferably 170° C. or less, more preferably165° C. or less, and still more preferably 160° C. or less.

By setting the polyamide glass transition temperature to be 90° C. ormore, a polyamide having excellent heat resistance and chemicalresistance can be obtained. By setting the polyamide glass transitiontemperature to be 170° C. or less, a molded product having a goodappearance can be obtained.

Measurement of the glass transition temperature can be carried out basedon JIS-K7121 as described in the below examples.

Examples of the glass transition temperature measurement apparatusinclude the Diamond-DSC, manufactured by PERKIN-ELMER Inc.

The polyamide according to the present embodiment preferably has a meltshear viscosity ηs of 20 to 140 Pa·s, more preferably 25 to 115 Pa·s,and still more preferably 30 to 90 Pa·s.

The melt shear viscosity can be measured based on the method describedin the below examples.

By setting the melt shear viscosity to be in the above-described range,a polyamide having excellent fluidity can be obtained.

The polyamide according to the present embodiment preferably has atensile strength of 70 MPa or more, more preferably 80 MPa or more, andstill more preferably 85 MPa or more.

Measurement of the tensile strength can be carried out based on ASTMD638 as described in the below examples.

By setting the tensile strength to be 70 MPa or more, a polyamide havingexcellent rigidity can be obtained.

The polyamide according to the present embodiment preferably has atensile elongation of 3.0% or more, more preferably 5.0% or more, andstill more preferably 7.0% or more.

Measurement of the tensile elongation can be carried out based on ASTMD638 as described in the below examples.

By setting the tensile elongation to be 3.0% or more, a polyamide havingexcellent toughness can be obtained.

The polyamide according to the present embodiment preferably has a waterabsorbance of 5.0% or less, more preferably 4.0% or less, and still morepreferably 3.0% or less.

Measurement of the water absorbance can be carried out based on themethod described in the below examples.

By setting the water absorbance to be 5.0% or less, a polyamidecomposition having excellent low water absorbance can be obtained.

The polyamide according to the present embodiment preferably has a colortone b value of 0 or less, and more preferably −2 or less.

The color tone b value can be measured by the method described in thebelow examples.

By setting the color tone b value to be 0 or less, a polyamidecomposition having excellent resistance to heat discoloration can beobtained.

(B) Inorganic Filler

The polyamide composition according to the present embodiment is apolyamide composition comprising the above-described (A) polyamide and a(B) inorganic filler.

As a polyamide composition, by comprising the (B) inorganic filler, apolyamide composition can be obtained having especially excellentrigidity while satisfying heat resistance, fluidity, toughness, and lowwater absorbance, without harming the polyamide qualities of havingexcellent heat resistance, fluidity, toughness, low water absorbance,rigidity and the like.

Polyamides such as PA6 and PA66 cannot satisfy these requirements interms of heat resistance, since their melting point is low.

The polyamide composition also has excellent light fastness and colortone as a polyamide composition, despite comprising the inorganicfiller.

The (B) inorganic filler used in the present embodiment is notespecially limited. Examples thereof include a glass fiber, a carbonfiber, a calcium silicate fiber, a potassium titanate fiber, an aluminumborate fiber, glass flakes, talc, kaolin, mica, hydrotalcite, calciumcarbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate,wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide,titanium oxide, silicon oxide, magnesium oxide, calcium silicate, sodiumaluminosilicate, magnesium silicate, Ketchen black, acetylene black,furnace black, carbon nanotubes, graphite, brass, copper, silver,aluminum, nickel, iron, calcium fluoride, isinglass, montmorillonite,expandable fluorine mica, and an apatite.

As the inorganic filler, one kind may be used, or two or more kinds maybe used in combination.

From perspectives such as rigidity and strength, a glass fiber, a carbonfiber, glass flakes, talc, kaolin, mica, calcium carbonate, calciummonohydrogen phosphate, wollastonite, silica, carbon nanotubes,graphite, calcium fluoride, montmorillonite, expandable fluorine mica,and an apatite are preferred as the (B) inorganic filler.

More preferably, the (B) inorganic filler is a glass fiber or a carbonfiber. Among glass fibers and carbon fibers, those having a numberaverage fiber diameter of 3 to 30 μm, a weight average fiber length of100 to 750 μm, and an aspect ratio (L/D) of number average fiber lengthto number average fiber diameter of from 10 to 100 may be preferablyused from the perspective of exhibiting high properties.

Further, wollastonite is more preferred as the (B) inorganic filler.Among wollastonites, a wollastonite having a number average fiberdiameter of 3 to 30 μm, a weight average fiber length of 10 to 500 μm,and an aspect ratio (L/D) of from 3 to 100 may be more preferably used.

In addition, as the (B) inorganic filler, talc, mica, kaolin, siliconnitride and the like are more preferred. Even among talc, mica, kaolin,silicon nitride and the like, those having a number average fiberdiameter of 0.1 to 3 μm may be more preferably used.

Measurement of the number average fiber diameter and the weight averagefiber length of the inorganic filler may be determined by dissolving amolded product of the polyamide composition in a solvent in which thepolyamide dissolves, such as formic acid, arbitrarily selecting 100 ormore, for example, of the inorganic filler particles from the obtainedinsoluble component, and observing these selected particles with anoptical microscope, a scanning electron microscope or the like.

A method for producing the polyamide composition according to thepresent embodiment is not especially limited, as long as it is a methodwhich mixes the above-described (A) polyamide and (B) inorganic filler.

Examples of the method for mixing the polyamide and the inorganic fillerinclude mixing the polyamide and the inorganic filler using a Henschelmixer or the like, then feeding the resultant mixture to a melt kneaderand kneading, and blending the inorganic filler in the polyamide turnedinto a melt state by a single-screw or twin-screw extruder from a sidefeeder.

The method for feeding the components constituting the polyamidecomposition may be carried out by feeding all of the constituentcomponents all at once to the same feed opening, or by feeding fromdifferent feed openings for each constituent component.

The melt kneading temperature is preferably about 250 to 375° C. at aresin temperature.

The melt kneading time is preferably about 0.5 to 5 minutes.

The apparatus for performing the melt kneading is not especiallylimited. Known apparatuses, for example, a melt kneader such as asingle-screw or twin-screw extruder, a Banbury mixer, and a mixing roll,may be used.

A blend amount of the (B) inorganic filler is preferably 0.1 to 200parts by mass, more preferably 1 to 180 parts by mass, and still morepreferably 5 to 150 parts by mass, based on 100 parts by mass of the (A)polyamide.

By setting the blend amount to 0.1 parts by mass or more, mechanicalproperties such as toughness and rigidity of the polyamide compositionimprove in a good manner. Further, by setting the blend amount to 200parts by mass or less, a polyamide composition having excellentmoldability can be obtained.

To the extent that the object of the present embodiment is not harmed,the polyamide composition comprising the (B) inorganic filler maycomprise additives which are customarily used in polyamides, such as apigment, a dye, a fire retardant, a lubricant, a fluorescent bleachingagent, a plasticizing agent, an organic antioxidant, a stabilizer, anultraviolet absorber, a nucleating agent, rubber, and a reinforcement.

A relative viscosity ηr at 25° C., A melting point Tm2, and A glasstransition temperature Tg of the polyamide composition comprising the(B) inorganic filler according to the present embodiment can be measuredby the same methods as the measurement methods for the above-describedpolyamide. Further, by setting the measurement values for the polyamidecomposition comprising the (B) inorganic filler in the same ranges asthe ranges preferred for the measurement values of the above-describedpolyamide, a polyamide composition having excellent heat resistance,moldability, and chemical resistance can be obtained.

The polyamide composition comprising the (B) inorganic filler preferablyhas a melt shear viscosity ηs of 30 to 200 Pa·s, more preferably 40 to180 Pa·s, and still more preferably 50 to 150 Pa·s.

The melt shear viscosity can be measured based on the method describedin the below examples.

By setting the melt shear viscosity to be in the above-described range,a polyamide composition having excellent fluidity can be obtained.

The polyamide composition comprising the (B) inorganic filler preferablyhas a tensile strength of 140 MPa or more, more preferably 150 MPa ormore, and still more preferably 160 MPa or more.

Measurement of the tensile strength can be carried out based on ASTMD638 as described in the below examples.

By setting the tensile strength to be 140 MPa or more, a polyamidecomposition having excellent rigidity can be obtained.

The polyamide composition comprising the (B) inorganic filler preferablyhas a tensile elongation of 1.0% or more, more preferably 1.5% or more,and still more preferably 2.0% or more.

Measurement of the tensile elongation can be carried out based on ASTMD638 as described in the below examples.

By setting the tensile elongation to be 1.0% or more, a polyamidecomposition having excellent toughness can be obtained.

The polyamide composition comprising the (B) inorganic filler preferablyhas a water absorbance of 5.0% or less, more preferably 4.0% or less,and still more preferably 3.0% or less.

Measurement of the water absorbance can be carried out based on themethod described in the below examples.

By setting the water absorbance to be 5.0% or less, a polyamidecomposition having excellent low water absorbance can be obtained.

(C) Copper Compound and Metal Halide

The polyamide composition according to the present embodiment is apolyamide composition which comprises the above-described (A) polyamideand a (C) copper compound and metal halide.

As a polyamide composition, by comprising a (C) copper compound andmetal halide, a polyamide composition can be obtained having excellentheat resistance, fluidity, toughness, low water absorbance, andrigidity, as well as excellent heat aging resistance, without harmingthe polyamide qualities of having excellent heat resistance, fluidity,toughness, low water absorbance, rigidity and the like.

Examples of the copper compound used in the present embodiment includecopper halide, copper acetate, copper propionate, copper benzoate,copper adipate, copper terephthalate, copper isophthalate, coppersalicylate, copper nicotinate, copper stearate, and copper complex saltscoordinated to a chelating agent such as ethylenediamine, andethylenediaminetetraacetic acid.

As the copper compound, preferred are copper iodide, copper(I) bromide,copper(II) bromide, copper(I) chloride, and copper acetate, and morepreferred are copper iodide and/or copper acetate, due to theirexcellent heat aging resistance and ability to suppress metal corrosionof the screw and cylinder parts (hereinafter, sometimes referred to as“metal corrosion”) during extrusion.

As the copper compound, one kind may be used, or two or more kinds maybe used in combination.

A blend amount of the copper compound in the polyamide composition ispreferably 0.01 to 0.6 parts by mass, and more preferably 0.02 to 0.4parts by mass, based on 100 parts by mass of the (A) polyamide.

By setting the blend amount of the copper compound in theabove-described range, sufficient heat aging resistance improves andcopper precipitation and metal corrosion can be suppressed.

It is preferred to comprise the copper compound so that, based on 10⁶parts by mass of the polyamide, the copper content is preferably 50 to2,000 parts by mass, more preferably 100 to 1,500 parts by mass, andstill more preferably 150 to 1,000 parts by mass.

By comprising 50 to 2,000 parts by mass of copper in the polyamidecomposition, a polyamide composition having excellent heat agingresistance can be obtained.

Examples of the metal halide used in the present embodiment excludecopper halides.

The metal halide is a salt of a Group 1 or 2 metal element in theperiodic table with a halogen. Examples thereof include potassiumiodide, potassium bromide, potassium chloride, sodium iodide, and sodiumchloride. Potassium iodide and potassium bromide are preferred.

As the metal halide, one kind may be used, or two or more kinds may beused in combination.

Potassium iodide is preferred as the metal halide, due to its excellentheat aging resistance and ability to suppress metal corrosion.

A blend amount of the metal halide in the polyamide composition ispreferably 0.05 to 20 parts by mass, and more preferably 0.2 to 10 partsby mass, based on 100 parts by mass of the (A) polyamide.

By setting the blend amount of the metal halide in the above-describedrange, sufficient heat aging resistance improves and copperprecipitation and metal corrosion can be suppressed.

It is preferred to comprise the copper compound and the metal halide inthe polyamide composition so that the ratio between the copper compoundand the metal halide has a halogen and copper molar ratio(halogen/copper) of from 2/1 to 50/1. The halogen and copper molar ratio(halogen/copper) is more preferably 2/1 to 40/1, and still morepreferably 5/1 to 30/1.

It is preferred that the halogen and copper molar ratio is 2/1 or more,because copper precipitation and metal corrosion can be suppressed.Further, if the halogen and copper molar ratio is 50/1 or less, theproblem of corrosion of the molding machine screw and the like can besuppressed, without harming mechanical properties such as toughness andrigidity.

Although advantageous effects can be obtained even if the coppercompound and the metal halide are respectively used by themselves, inthe present embodiment it is preferred to blend both of these componentsin order to improve the performance of the obtained polyamidecomposition.

Examples of the method for producing the polyamide composition accordingto the present embodiment include, for example, adding the (C) coppercompound and metal halide individually or as a mixture during thepolymerization step of the (A) polyamide (hereinafter, sometimesabbreviated as “production method 1”), and adding the (C) coppercompound and metal halide individually or as a mixture to the (A)polyamide using melt kneading (hereinafter, sometimes abbreviated as“production method 2”).

In the method for producing the polyamide composition, when adding the(C) copper compound and metal halide, these may be added as is as asolid or in an aqueous solution state.

The “polymerization step of the polyamide” in production method 1 refersto any of the steps until completion of polymerization of the polyamidefrom the raw material monomers. The addition may be carried out at anystage.

The apparatus for performing the melt kneading in production method 2 isnot especially limited. Known apparatuses, for example, a melt kneadersuch as single-screw or twin-screw extruder, a Banbury mixer, and amixing roll, may be used.

Of these, it is preferred to use a twin-screw extruder.

The melt kneading temperature is preferably a temperature about 1 to100° C. higher than the melting point of the (A) polyamide, and morepreferably about 10 to 50° C. higher.

A shear rate in the kneader is preferably about 100 sec⁻¹ or more. Anaverage dwell time during the kneading is preferably about 0.5 to 5minutes.

To the extent that the object of the present embodiment is not harmed,other additives may be added for dispersing the copper compound and themetal halide in the polyamide.

Examples of these other additives include, as a lubricant, higher fattyacids such as lauryl acid, higher fatty acid metal salts of a higherfatty acid and a metal such as aluminum, higher fatty acid amides suchas N,N-ethylenebis(stearamide), and waxes such as polyethylene wax.

Further examples thereof include organic compounds having at least oneamide group.

By further comprising the (B) inorganic filler in the polyamidecomposition comprising the (C) copper compound and metal halide, apolyamide composition having even better mechanical properties, such astoughness and rigidity, can be obtained.

A blend amount of the inorganic filler is preferably 0.1 to 200 parts bymass, more preferably 1 to 180 parts by mass, and still more preferably5 to 150 parts by mass, based on 100 parts by mass of the polyamide.

By setting the blend amount of the inorganic filler to 0.1 parts by massor more, mechanical properties such as toughness and rigidity of thepolyamide composition improve in a good manner. Further, by setting theblend amount of the inorganic filler to 200 parts by mass or less, apolyamide composition having excellent moldability can be obtained.

To the extent that the object of the present embodiment is not harmed,the polyamide composition comprising the (C) copper compound and metalhalide may comprise additives which are customarily used in polyamides,such as a pigment, a dye, a fire retardant, a lubricant, a fluorescentbleaching agent, a plasticizing agent, an organic antioxidant, astabilizer, an ultraviolet absorber, a nucleating agent, rubber, and areinforcement.

A relative viscosity it at 25° C., a melting point Tm2, and a glasstransition temperature Tg of the polyamide composition comprising the(C) copper compound and metal halide according to the present embodimentcan be measured by the same methods as the measurement methods for theabove-described polyamide. Further, by setting the measurement valuesfor the polyamide composition comprising the (C) copper compound andmetal halide in the same ranges as the ranges preferred for themeasurement values of the above-described polyamide, a polyamidecomposition having excellent heat resistance, moldability, and chemicalresistance can be obtained.

The polyamide composition comprising the (C) copper compound and metalhalide preferably has a melt shear viscosity ηs of 30 to 200 Pa·s, morepreferably 40 to 180 Pa·s, and still more preferably 50 to 150 Pa·s.

The melt shear viscosity can be measured based on the method describedin the below examples.

By setting the melt shear viscosity to be in the above-described range,a polyamide composition having excellent fluidity can be obtained.

The polyamide composition comprising the (C) copper compound and metalhalide preferably has a tensile strength of 140 MPa or more, morepreferably 150 MPa or more, and still more preferably 160 MPa or more.

Measurement of the tensile strength can be carried out based on ASTMD638 as described in the below examples.

By setting the tensile strength to be 140 MPa or more, a polyamidecomposition having excellent rigidity can be obtained.

The polyamide composition comprising the (C) copper compound and metalhalide preferably has a tensile elongation of 1.0% or more, morepreferably 1.5% or more, and still more preferably 2.0% or more.

Measurement of the tensile elongation can be carried out based on ASTMD638 as described in the below examples.

By setting the tensile elongation to be 1.0% or more, a polyamidecomposition having excellent toughness can be obtained.

The polyamide composition comprising the (C) copper compound and metalhalide preferably has a water absorbance of 5.0% or less, morepreferably 4.0% or less, and still more preferably 3.0% or less.

Measurement of the water absorbance can be carried out based on themethod described in the below examples.

By setting the water absorbance to be 5.0% or less, a polyamidecomposition having excellent low water absorbance can be obtained.

The polyamide composition comprising the (C) copper compound and metalhalide preferably has, as a molded product, a strength half-life of 40days or more, more preferably 45 days or more, and still more preferably50 days or more.

Measurement of the strength half-life can be carried out based on themethod described in the below examples.

By setting the strength half-life to be 40 days or more, a polyamidecomposition having excellent heat resistance, and especially excellentheat aging resistance, can be obtained.

The polyamide composition comprising the (C) copper compound and metalhalide preferably has a breaking stress of 45 MPa or more, morepreferably 50 MPa or more, and still more preferably 55 MPa or more.

Measurement of the breaking stress can be carried out based on themethod described in the below examples.

By molding a polyamide composition having a breaking stress of 45 MPa ormore, a polyamide composition having excellent vibration fatigueresistance can be obtained.

The polyamide composition comprising the (C) copper compound and metalhalide preferably has a tensile strength retention rate after dipping of60% or more, more preferably 75% or more, and still more preferably 80%or more.

Measurement of the tensile strength retention rate after dipping can becarried out based on the method described in the below examples.

By molding a polyamide composition having a tensile strength retentionrate after dipping of 60% or more, a polyamide composition havingexcellent LLC resistance can be obtained.

(D) Halogen-Based Flame Retardant

The polyamide composition according to the present embodiment is apolyamide composition which comprises the above-described (A) polyamideand a (D) halogen-based flame retardant.

As the polyamide composition according to the present embodiment, bycomprising the (D) halogen-based flame retardant, a polyamidecomposition can be obtained having excellent heat resistance, fluidity,toughness, rigidity, and low water absorbance, as well as excellentflame resistance, without harming the polyamide qualities of havingexcellent heat resistance, fluidity, toughness, rigidity, and low waterabsorbance.

Further, even though the polyamide composition according to the presentembodiment comprises a halogen-based flame retardant, it has excellentlight fastness, and even has excellent color tone as a polyamidecomposition.

The (D) halogen-based flame retardant used in the present embodiment isnot especially limited, as long as it is a flame retardant whichcomprises a halogen element. Examples thereof include chlorine-basedflame retardants and bromine-based flame retardants, for example.

As such a flame retardant, one kind may be used, or two or more kindsmay be used in combination.

Examples of chlorine-based flame retardants include chlorinatedparaffin, chlorinated polyethylene,dodecachloropentacyclooctadeca-7,15-diene (Dechlorane Plus 25®,manufactured by Occidental Corporation), and HET anhydride.

Examples of bromine-based flame retardants includehexabromocyclododecane (HBCD), decabromodiphenyl oxide (DBDPO),octabromodiphenyl oxide, tetrabromobisphenol A (TBBA),bis(tribromophenoxy)ethane, bis(pentabromophenoxy)ethane (BPBPE), atetrabromobisphenol A epoxy resin (TBBA epoxy), a tetrabromobisphenol Acarbonate (TBBA-PC), ethylene(bistetrabromophthal)imide (EBTBPI),ethylenebispentabromodiphenyl, tris(tribromophenoxy)triazine (TTBPTA),bis(dibromopropyl)tetrabromobisphenol A (DBP-TBBA),bis(dibromopropyl)tetrabromobisphenol S (DBP-TBBS), brominatedpolyphenylene ether (including poly(di)bromophenylene ether etc.)(BrPPE), brominated polystyrene (including polydibromostyrene,polytribromostyrene, crosslinked brominated polystyrene etc.) (BrPS),brominated crosslinked aromatic polymers, brominated epoxy resins,brominated phenoxy resins, brominated styrene-maleic anhydride polymers,tetrabromobisphenol S (TBBS), tris(tribromoneopentyl)phosphate (TTBNPP),polybromotrimethylphenylindan (PBPI), andtris(dibromopropyl)-isocyanurate (TDBPIC).

From the perspective that an amount of corrosive gases produced duringmelt processing such as extrusion and molding is low, exhibition offlame resistance, and mechanical properties such as toughness andrigidity, the (D) halogen-based flame retardant is preferably abrominated polyphenylene ether (including poly(di)bromophenylene etheretc.) and a brominated polystyrene (including polydibromostyrene,polytribromostyrene, crosslinked brominated polystyrene etc.). Abrominated polystyrene is more preferred.

The brominated polystyrene is not especially limited, and may beproduced, for example, by polymerizing a styrene monomer to produce apolystyrene, and then brominating a benzene ring on the polystyrene.Alternatively, the brominated polystyrene may be produced bypolymerizing a brominated styrene monomer (bromostyrene, dibromostyrene,tribromostyrene etc.).

A bromine content in the brominated polystyrene is preferably 55 to 75mass %. By setting the bromine content to 55 mass % or more, the bromineamount required for achieving flame resistance can be satisfied with asmall brominated polystyrene blend amount, and a polyamide compositionhaving excellent heat resistance, fluidity, toughness, low waterabsorbance, and rigidity, as well as excellent flame resistance, can beobtained without harming the qualities possessed by a polyamide.Further, by setting the bromine content to 75 mass % or less, apolyamide composition can be obtained which is not easily pyrolyzedduring melt processing such as extrusion and molding, can suppress gasoccurrence and the like, and has excellent resistance to heatdiscoloration.

The polyamide composition comprising the (D) halogen-based flameretardant may also further comprise any of a (G) flame retardantauxiliary, a (H) polymer comprising an α,β-unsaturated dicarboxylic acidanhydride, and the (B) inorganic filler.

By further comprising the (G) flame retardant auxiliary in the polyamidecomposition comprising the (D) halogen-based flame retardant, apolyamide composition having even better flame resistance can beobtained.

The (G) flame retardant auxiliary used in the present embodiment is notespecially limited. Examples thereof may include antimony oxides such asdiantimony trioxide, diantimony tetroxide, diantimony pentoxide, andsodium antimonate; tin oxides such as tin monoxide and tin dioxide; ironoxides such as iron(II) oxide and γ-iron oxide; other metal oxides suchas zinc oxide, zinc borate, calcium oxide, aluminum oxide (alumina),aluminum oxide (boehmite), silicon oxide (silica), titanium oxide,zirconium oxide, manganese oxide, molybdenum oxide, cobalt oxide,bismuth oxide, chromium oxide, tin oxide, nickel oxide, copper oxide,and tungsten oxide; metal hydroxides such as magnesium hydroxide andaluminum hydroxide; metal powders of aluminum, iron, titanium,manganese, zinc, molybdenum, cobalt, bismuth, chromium, tin, antimony,nickel, copper, tungsten and the like; metal carbonates such as zinccarbonate, calcium carbonate, magnesium carbonate, and barium carbonate;metal borates such as magnesium borate, calcium borate, aluminum borate;and silicone.

As the (G) flame retardant auxiliary, one kind may be used, or two ormore kinds may be used in combination.

From the perspective of the flame resistance effect, the (G) flameretardant auxiliary used along with the (D) halogen-based flameretardant is preferably an antimony oxide such as diantimony trioxide,diantimony tetroxide, diantimony pentoxide, and sodium antimonate, a tinoxide such as tin monoxide and tin dioxide, an iron oxide such asiron(II) oxide and γ-iron oxide, zinc oxide, and zinc borate. Morepreferred are an antimony oxide such as diantimony trioxide, diantimonytetroxide, and diantimony pentoxide, and zinc borate, and still morepreferred is diantimony trioxide.

To increase the flame retardance effect, it is preferred to use a (G)flame retardant auxiliary having an average particle size of 0.01 to 10μm.

The average particle size may be measured using a laserdiffraction/scattering type particle size distribution analyzer or aprecise particle size distribution analyzer.

By further comprising the (H) polymer comprising the α,β-unsaturateddicarboxylic acid anhydride in the polyamide composition comprising the(D) halogen-based flame retardant, a polyamide composition havingexcellent flame resistance and also mechanical properties such astoughness and rigidity can be obtained.

Examples of the (H) polymer comprising the α,β-unsaturated dicarboxylicacid anhydride used in the present embodiment include a polymercomprising the α,β-unsaturated dicarboxylic acid anhydride as acopolymer component, and a polymer modified with the α,β-unsaturateddicarboxylic acid anhydride.

Examples of the α,β-unsaturated dicarboxylic acid anhydride include thecompounds represented by the following general formula (1).

In general formula (1), R¹ and R² are each independently a hydrogen oran alkyl group having 1 to 3 carbon atoms.

Examples of the α,β-unsaturated dicarboxylic acid anhydride includemaleic anhydride and methyl maleic anhydride. Maleic anhydride ispreferred.

Examples of the polymer comprising the α,β-unsaturated dicarboxylic acidanhydride as a copolymer component include a copolymer of an aromaticvinyl compound and an α,β-unsaturated dicarboxylic acid anhydride.

Examples of the polymer modified with the α,β-unsaturated dicarboxylicacid anhydride include a polyphenylene ether resin and a polypropyleneresin modified with an α,β-unsaturated dicarboxylic acid anhydride.

From the perspective of efficiency in improving flame retardance(exhibiting flame retardance with a small added amount), a copolymer ofan aromatic vinyl compound and an α,β-unsaturated dicarboxylic acidanhydride is preferred as the (H) polymer comprising an α,β-unsaturateddicarboxylic acid anhydride.

Examples of the aromatic vinyl compound used in the present embodimentinclude the compounds represented by the following general formula (2).

In general formula (2), R³ and R⁴ are each independently a hydrogen oran alkyl group having 1 to 3 carbon atoms, and k denotes an integer of 1to 5.

Examples of the aromatic vinyl compound include styrene,α-methylstyrene, and p-methylstyrene. Styrene is preferred.

In the present embodiment, when the polymer comprising theα,β-unsaturated dicarboxylic acid anhydride comprises the aromatic vinylcompound component, it is thought that the aromatic vinyl compoundcomponent has an affinity with the halogen-based flame retardant(brominated polystyrene etc.), and assists in the dispersion of thehalogen-based flame retardant in the polyamide matrix, thereby allowingfiner dispersion of the halogen-based flame retardant, due to theα,β-unsaturated dicarboxylic acid anhydride component having an affinitywith or reacting with the polyamide.

From perspectives such as flame resistance, fluidity, and resistance topyrolysis, the ratio of the aromatic vinyl compound component and theα,β-unsaturated dicarboxylic acid anhydride component in the copolymerof the aromatic vinyl compound and the α,β-unsaturated dicarboxylic acidanhydride is preferably set so that the aromatic vinyl compoundcomponent is 50 to 99 mass %, and the α,β-unsaturated dicarboxylic acidanhydride component is 1 to 50 mass %. The ratio of the α,β-unsaturateddicarboxylic acid anhydride component is more preferably 5 to 20 mass %,and still more preferably 8 to 15 mass %.

By setting the ratio of the α,β-unsaturated dicarboxylic acid anhydridecomponent to 1 mass % or more, a polyamide composition having excellentmechanical properties such as toughness and rigidity as well asexcellent flame resistance can be obtained. Further, by setting theratio of the α,β-unsaturated dicarboxylic acid anhydride component to 50mass % or less, deterioration of the polyamide composition due to theα,β-unsaturated dicarboxylic acid anhydride can be prevented.

By comprising the above-described (B) inorganic filler in the polyamidecomposition comprising the (D) halogen-based flame retardant, apolyamide composition having excellent mechanical properties such astoughness and rigidity can be obtained.

A method for producing the polyamide composition according to thepresent embodiment is not especially limited, as long as the methodmixes the above-described (A) polyamide and the (D) halogen-based flameretardant. Further, examples of the method for producing the polyamidecomposition comprising the (D) halogen-based flame retardant include amethod in which the (G) flame retardant auxiliary and the (H) polymercomprising the α,β-unsaturated dicarboxylic acid anhydride and/or the(B) inorganic filler are further mixed.

Examples of the method for mixing the polyamide and the halogen-basedflame retardant include mixing the polyamide and the halogen-based flameretardant, and optionally the flame retardant auxiliary, the polymercomprising the α,β-unsaturated dicarboxylic acid anhydride, and/or theinorganic filler, using a Henschel mixer and the like, feeding theresultant mixture to a melt kneader, and kneading. Another examplethereof includes forming in advance using a Henschel mixer and the likea mixture of the polyamide and the halogen-based flame retardant, andoptionally the flame retardant auxiliary and/or the polymer comprisingthe α,β-unsaturated dicarboxylic acid anhydride with a single-screw or atwin-screw extruder, feeding the resultant mixture to a melt kneader,kneading, and then, optionally, adding the inorganic filler from a sidefeeder.

The method for feeding the components constituting the polyamide can becarried out by feeding all of the constituent components all at once tothe same feed opening, or by feeding from different feed openings foreach constituent component.

The melt kneading temperature is preferably about 250 to 375° C. at aresin temperature.

The melt kneading time is preferably about 0.5 to 5 minutes.

As the apparatus for performing the melt kneading, it is preferred touse a known apparatus, for example a melt kneader such as a single-screwor twin-screw extruder, a Banbury mixer, and a mixing roll.

A blend amount of the (D) halogen-based flame retardant, and a blendamounts of the optional (G) flame retardant auxiliary, (H) polymercomprising an α,β-unsaturated dicarboxylic acid anhydride and/or (B)inorganic filler, are not especially limited.

The blend amount of the halogen-based flame retardant in the polyamidecomposition is preferably 30 to 60 parts by mass, more preferably 35 to55 parts by mass, and still more preferably 40 to 50 parts by mass,based on 100 parts by mass of the polyamide.

By setting the blend amount of the halogen-based flame retardant to be30 parts by mass or more, a polyamide composition having excellent heatresistance can be obtained. Further, by setting the blend amount of thehalogen-based flame retardant to be 60 parts by mass or less, theoccurrence of decomposition gases during melt kneading, deterioration influidity during molding processing, and adherence of a contaminatingsubstance to the mold die can be suppressed. In addition, deteriorationin mechanical properties such as toughness and rigidity anddeterioration in the molded product appearance can be suppressed.

A blend amount of the flame retardant auxiliary in the polyamidecomposition is preferably 0 to 30 parts by mass, more preferably 1 to 30parts by mass, still more preferably 2 to 20 parts by mass, and evenstill more preferably 4 to 15 parts by mass, based on 100 parts by massof the polyamide.

By blending the flame retardant auxiliary, a polyamide compositionhaving even better flame resistance can be obtained. Further, by settingthe blend amount of the flame retardant auxiliary to be 30 parts by massor less, the viscosity during melt processing can be controlled in asuitable range, an increase in torque during extrusion can besuppressed, and deterioration in moldability during molding processingand deterioration in the molded product appearance can be suppressed.Moreover, a polyamide composition having excellent toughness and thelike can be obtained without harming the polyamide qualities of havingexcellent mechanical properties such as toughness and rigidity.

A blend amount of the polymer comprising an α,β-unsaturated dicarboxylicacid anhydride in the polyamide composition is preferably 0 to 20 partsby mass, more preferably 0.5 to 20 parts by mass, still more preferably1 to 15 parts by mass, and even still more preferably 2 to 10 parts bymass, based on 100 parts by mass of the polyamide.

By blending the polymer comprising the α,β-unsaturated dicarboxylic acidanhydride, the fine dispersion effects of the halogen-based flameretardant in the polyamide due to compatibilizing effect can beincreased, so that a polyamide composition having an excellent effect inimproving flame resistance and strength can be obtained. Further, bysetting the blend amount of the polymer comprising the α,β-unsaturateddicarboxylic acid anhydride to be 20 parts by mass or less, a polyamidecomposition having excellent strength and the like can be obtainedwithout harming the polyamide qualities of having excellent mechanicalproperties such as toughness and rigidity.

A blend amount of the inorganic filler in the polyamide composition ispreferably 0 to 200 parts by mass, more preferably 0.1 to 200 parts bymass, still more preferably 1 to 180 parts by mass, and even still morepreferably 5 to 150 parts by mass based on 100 parts by mass of thepolyamide.

By blending the inorganic filler, mechanical properties such astoughness and rigidity of the polyamide composition improve in a goodmanner. Further, by setting the blend amount of the inorganic filler to200 parts by mass or less, a polyamide composition having excellentmoldability can be obtained.

To the extent that the object of the present embodiment is not harmed,the polyamide composition comprising the (D) halogen-based flameretardant may comprise additives which are customarily used inpolyamides, such as a pigment, a dye, a fire retardant, a lubricant, afluorescent bleaching agent, a plasticizing agent, an organicantioxidant, a stabilizer, an ultraviolet absorber, a nucleating agent,rubber, and a reinforcement.

A relative viscosity ηr at 25° C., a melting point Tm2, and a glasstransition temperature Tg of the polyamide composition comprising the(D) halogen-based flame retardant according to the present embodimentcan be measured by the same methods as the measurement methods for theabove-described polyamide. Further, by setting the measurement valuesfor the polyamide composition comprising the (D) halogen-based flameretardant in the same ranges as the ranges preferred for the measurementvalues of the above-described polyamide, a polyamide composition havingexcellent heat resistance, moldability, mechanical properties such astoughness and rigidity, and chemical resistance can be obtained.

The polyamide composition comprising the (D) halogen-based flameretardant preferably has a tensile strength of 140 MPa or more, morepreferably 150 MPa or more, and still more preferably 160 MPa or more.

Measurement of the tensile strength can be carried out based on ASTMD638 as described in the below examples.

By setting the tensile strength to be 140 MPa or more, a polyamidecomposition having excellent rigidity can be obtained.

The polyamide composition comprising the (D) halogen-based flameretardant preferably has a tensile elongation of 1.0% or more, morepreferably 1.5% or more, and still more preferably 2.0% or more.

Measurement of the tensile elongation can be carried out based on ASTMD638 as described in the below examples.

By setting the tensile elongation to be 1.0% or more, a polyamidecomposition having excellent toughness can be obtained.

The polyamide composition comprising the (D) halogen-based flameretardant preferably has a water absorbance of 5.0% or less, morepreferably 4.0% or less, and still more preferably 3.0% or less.

Measurement of the water absorbance can be carried out based on themethod described in the below examples.

By setting the water absorbance to be 5.0% or less, a polyamidecomposition having excellent low water absorbance can be obtained.

The flame resistance of the polyamide composition comprising the (D)halogen-based flame retardant is measured based on UL-94VB.

The polyamide composition preferably has a flame resistance of V-2 ormore, more preferably V-1 or more, and more preferably V-0.

The polyamide composition comprising the (D) halogen-based flameretardant preferably has a flow length of 15 cm or more, more preferably17 cm or more, and still more preferably 20 cm or more.

The flow length can be measured by the method described in the belowexamples.

By setting the flow length to 15 cm or more, a polyamide compositionhaving excellent fluidity can be obtained.

(E) Phosphinate and/or Diphosphinic Acid

The polyamide composition according to the present embodiment is apolyamide composition comprising the above-described (A) polyamide andan (E) phosphinate and/or diphosphinate (hereinafter, sometimescollectively referred to as “phosphinate”).

Examples of phosphinic acid include the compounds represented by thefollowing general formula (I).

Examples of diphosphinic acid include the compounds represented by thefollowing general formula (II).

In general formulae (I) and (II), R⁵ and R⁶, and R⁷ and R⁸, are eachindependently selected from the group consisting of an alkyl grouphaving 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms,and an arylalkyl group having 7 to 20 carbon atoms. R⁹ is selected fromthe group consisting of an alkylene group having 1 to 10 carbon atoms,an arylene group having 6 to 10 carbon atoms, an alkylarylene grouphaving 7 to 20 carbon atoms, and an arylalkylene group having 7 to 20carbon atoms. M is selected from the group consisting of calcium (ion),magnesium (ion), aluminum (ion), and zinc (ion), m is 2 or 3, n is 1 or3, and x is 1 or 2.

In the present embodiment, examples of the alkyl group includestraight-chain or branched saturated aliphatic groups.

In the present embodiment, examples of the aryl group include aromaticgroups, which are unsubstituted or substituted with varioussubstituents, having 6 to 20 carbon atoms, such as a phenyl group, abenzyl group, an o-toluoyl group, and a 2,3-xylyl group.

As the polyamide composition according to the present embodiment, bycomprising the (E) phosphinate, a polyamide composition can be obtainedhaving excellent heat resistance, fluidity, toughness, low waterabsorbance, and rigidity, as well as having excellent flame resistance,without harming the polyamide qualities of having excellent heatresistance, fluidity, toughness, low water absorbance, and rigidity.

Further, the polyamide composition according to the present embodimentalso has excellent light fastness and color tone as a polyamidecomposition, despite inclusion of the phosphinate.

The (E) phosphinate used in the present embodiment can be produced in anaqueous solution using phosphinic acid and a metal component, such as ametal carbonate, a metal hydroxide, or a metal oxide, as described inEuropean Patent Application Publication No. 699708 and Japanese PatentLaid-Open No. 8-73720.

Although such compounds are essentially monomeric compounds, dependingon the reaction conditions, polymeric phosphinates having a degree ofcondensation of 1 to 3 based on the environment are also included.

Examples of the phosphinic acid and diphosphinic acid for the (E)phosphinate include dimethylphosphinic acid, ethylmethylphosphinic acid,diethylphosphinic acid, methyl-n-propylphosphinic acid,methanedi(methylphosphinic acid), benzene-1,4-di(methylphosphinic acid),methylphenylphosphinic acid, and diphenylphosphinic acid.

Examples of the metal component for the (E) phosphinate include acalcium ion, a magnesium ion, an aluminum ion, and a zinc ion.

Examples of the (E) phosphinate include calcium dimethylphosphinate,magnesium dimethylphosphinate, aluminum dimethylphosphinate, zincdimethylphosphinate, calcium ethylmethylphosphinate, magnesiumethylmethylphosphinate, aluminum ethylmethylphosphinate, zincethylmethylphosphinate, calcium diethylphosphinate, magnesiumdiethylphosphinate, aluminum diethylphosphinate, zincdiethylphosphinate, calcium methyl-n-propylphosphinate, magnesiummethyl-n-propylphosphinate, aluminum methyl-n-propylphosphinate, zincmethyl-n-propylphosphinate, calcium methylenebis(methylphosphinate),magnesium methylenebis(methylphosphinate), aluminummethylenebis(methylphosphinate), zinc methylenebis(methylphosphinate),calcium phenylene-1,4-bis(methylphosphinate), magnesiumphenylene-1,4-bis(methylphosphinate), aluminumphenylene-1,4-bis(methylphosphinate), zincphenylene-1,4-bis(methylphosphinate), calcium methylphenylphosphinate,magnesium methylphenylphosphinate, aluminum methylphenylphosphinate,zinc methylphenylphosphinate, calcium diphenylphosphinate, magnesiumdiphenylphosphinate, aluminum diphenylphosphinate, and zincdiphenylphosphinate.

As the (E) phosphinate, one kind may be used, or two or more kinds maybe used in combination.

From the perspectives of the flame resistance and the electricproperties of the polyamide composition, and also from the perspectiveof phosphinate synthesis, the (E) phosphinate is preferably calciumdimethylphosphinate, aluminum dimethylphosphinate, zincdimethylphosphinate, calcium ethylmethylphosphinate, aluminumethylmethylphosphinate, zinc ethylmethylphosphinate, calciumdiethylphosphinate, aluminum diethylphosphinate, and zincdiethylphosphinate.

From the perspectives of mechanical properties such as toughness andrigidity and of the appearance of the molded product obtained by moldingthe polyamide composition, it is preferred to use the (E) phosphinate asa powder ground to a particle size of 100 μm or less, and morepreferably as a powder ground to a particle size of from 50 μm or less.

It is preferred to use the (E) phosphinate as a powder having a particlesize of 0.5 to 20 μm, because not only does this allow a polyamidecomposition which exhibits high flame resistance to be obtained, but thestrength of the molded product is also substantially increased.

The average particle size may be measured using a laserdiffraction/scattering type particle size distribution analyzer or aprecise particle size distribution analyzer.

The (E) phosphinate does not have to be a completely pure. It isacceptable for certain amounts of unreacted products or byproducts toremain.

The polyamide composition comprising the (E) phosphinate may alsofurther comprise any of the (G) flame retardant auxiliary and the (B)inorganic filler.

By further comprising the (G) flame retardant auxiliary in the polyamidecomposition comprising the (E) phosphinate, a polyamide compositionhaving even better flame resistance can be obtained.

The (G) flame retardant auxiliary is not especially limited, as long asit a flame retardant auxiliary described above. Of those, preferred aremetal oxides such as zinc oxide, iron oxide, calcium oxide, aluminumoxide (alumina), aluminum oxide (boehmite), silicon oxide (silica),titanium oxide, zirconium oxide, manganese oxide, molybdenum oxide,cobalt oxide, bismuth oxide, chromium oxide, tin oxide, antimony oxide,nickel oxide, copper oxide, and tungsten oxide, metal hydroxides such asmagnesium hydroxide and aluminum hydroxide, metal powders of aluminum,iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium,tin, antimony, nickel, copper, tungsten and the like, metal carbonatessuch as zinc carbonate, calcium carbonate, magnesium carbonate, andbarium carbonate, metal borates such as zinc borate, magnesium borate,calcium borate, aluminum borate, and silicone.

As the (G) flame retardant auxiliary, one kind may be used, or two ormore kinds may be used in combination.

From the perspective of flame resistance, as the (G) flame retardantauxiliary used with the (E) phosphinate, preferred are calcium oxide,aluminum oxide (alumina), aluminum hydroxide (boehmite), magnesiumhydroxide, and zinc borate.

As the zinc borate, more preferred is a zinc borate represented byxZnO.yB₂O₃.zH₂O (wherein x>0, y>0, and z≧0). Still more preferred are2ZnO.3B₂O₃.3.5H₂O, 4ZnO.B₂O₃—H₂O, and 2ZnO.3B₂O.

These zinc borate compounds may be treated with a surface treatmentagent such as a silane coupling agent and a titanate coupling agent.

The flame retardant auxiliary preferably has a particle size of 30 μm orless, more preferably 15 μm or less, and still more preferably 7 μm orless.

A blend amount of the (E) phosphinate and a blend amounts of theoptional (G) flame retardant auxiliary and/or (B) inorganic filler, inthe polyamide composition according to the present embodiment are notespecially limited.

The blend amount of the phosphinate in the polyamide composition ispreferably 20 to 90 parts by mass, more preferably 25 to 80 parts bymass, and still more preferably 30 to 60 parts by mass, based on 100parts by mass of the polyamide.

By setting the blend amount of the phosphinate to be 20 parts by mass ormore, a polyamide composition having excellent flame resistance can beobtained. Further, by setting the blend amount of the phosphinate to be90 parts by mass or less, deterioration in fluidity during moldingprocessing can be suppressed. In addition, deterioration in mechanicalproperties such as toughness and rigidity and deterioration in themolded product appearance can be suppressed.

A blend amount of the flame retardant auxiliary in the polyamidecomposition is preferably 0 to 30 parts by mass, more preferably 1 to 30parts by mass, still more preferably 1 to 20 parts by mass, and evenstill more preferably 2 to 15 parts by mass, based on 100 parts by massof the polyamide.

By blending the flame retardant auxiliary, a polyamide compositionhaving even better flame resistance can be obtained. Further, by settingthe blend amount of the flame retardant auxiliary to be 30 parts by massor less, the viscosity during melt processing can be controlled in asuitable range, an increase in torque during extrusion can besuppressed, and deterioration in moldability during molding processingand deterioration in the molded product appearance can be suppressed.Moreover, a polyamide composition having excellent toughness can beobtained without harming the polyamide qualities of having excellentmechanical properties such as toughness and rigidity.

A blend amount of the inorganic filler in the polyamide composition ispreferably 0 to 200 parts by mass, more preferably 0.1 to 200 parts bymass, still more preferably 1 to 180 parts by mass, and even still morepreferably 5 to 150 parts by mass, based on 100 parts by mass of thepolyamide.

By further blending the inorganic filler, mechanical properties such astoughness and rigidity of the polyamide composition improve in a goodmanner. Further, by setting the blend amount of the inorganic filler to200 parts by mass or less, a polyamide composition having excellentmoldability can be obtained.

To the extent that the object of the present embodiment is not harmed,the polyamide composition comprising the (E) phosphinate may compriseadditives which are customarily used in polyamides, such as a pigment, adye, a fire retardant, a lubricant, a fluorescent bleaching agent, aplasticizing agent, an organic antioxidant, a stabilizer, an ultravioletabsorber, a nucleating agent, rubber, and a reinforcement.

A relative viscosity ηr at 25° C., a melting point Tm2, and a glasstransition temperature Tg of the polyamide composition comprising the(E) phosphinate can be measured by the same methods as the measurementmethods for the above-described polyamide. Further, by setting themeasurement values for the polyamide composition comprising the (E)phosphinate in the same ranges as the ranges preferred for themeasurement values of the above-described polyamide, a polyamidecomposition having excellent heat resistance, moldability, mechanicalproperties such as toughness and rigidity, and chemical resistance canbe obtained.

The polyamide composition comprising the (E) phosphinate preferably hasa tensile strength of 140 MPa or more, more preferably 150 MPa or more,and still more preferably 160 MPa or more.

Measurement of the tensile strength can be carried out based on ASTMD638 as described in the below examples.

By setting the tensile strength to be 140 MPa or more, a polyamidecomposition having excellent rigidity can be obtained.

The polyamide composition comprising the (E) phosphinate preferably hasa tensile elongation of 1.0% or more, more preferably 1.5% or more, andstill more preferably 2.0% or more.

Measurement of the tensile elongation can be carried out based on ASTMD638 as described in the below examples.

By setting the tensile elongation to be 1.0% or more, a polyamidecomposition having excellent toughness can be obtained.

The polyamide composition comprising the (E) phosphinate preferably hasa water absorbance of 5.0% or less, more preferably 4.0% or less, andstill more preferably 3.0% or less.

Measurement of the water absorbance can be carried out based on themethod described in the below examples.

By setting the water absorbance to be 5.0% or less, a polyamidecomposition having excellent low water absorbance can be obtained.

A flame resistance of the polyamide composition comprising the (E)phosphinate is measured based on UL-94VB. The polyamide compositionpreferably has a flame resistance of V-2 or more, more preferably V-1 ormore, and more preferably V-0.

The polyamide composition comprising the (E) phosphinate preferably hasa full filling pressure of 15 to 50%, more preferably 18 to 48%, andstill more preferably 20 to 45%.

The full filling pressure can be measured by the method described in thebelow examples.

By setting the full filling pressure in the above-described range, apolyamide composition having excellent fluidity can be obtained.

(F) Stabilizer

The polyamide composition according to the present embodiment is apolyamide composition which comprises the above-described (A) polyamideand an (F) stabilizer.

As the polyamide composition according to the present embodiment, bycomprising the (F) stabilizer, a polyamide composition can be obtainedhaving excellent heat resistance, fluidity, toughness, low waterabsorbance, and rigidity, as well as excellent resistance to heatdiscoloration and weatherability, without harming the polyamidequalities of having excellent heat resistance, fluidity, toughness, lowwater absorbance, and rigidity.

The (F) stabilizer used in the present embodiment is at least one kindselected from the group consisting of phenolic-based stabilizers,phosphite-based stabilizers, hindered amine-based stabilizers,triazine-based stabilizers, sulfur-based stabilizers, and inorganicphosphorus-based stabilizers.

As the stabilizer, one kind may be used, or two or more kinds may beused in combination.

Examples of phenolic-based stabilizers are not especially limited, andmay include hindered phenol compounds.

Examples of hindered phenol compounds includeN,N′-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionamide)],pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],N,N′-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide),triethyleneglycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],3,9-bis{2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane,3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester,1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate.

As the phenolic-based stabilizer, one kind may be used, or two or morekinds may be used in combination.

Examples of phosphite-based stabilizers are not especially limited, andmay include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite,octyldiphenyl phosphite, trisisodecyl phosphite, phenyl diisodecylphosphite, phenyl di(tridecyl) phosphite, diphenyl isooctyl phosphite,diphenyl isodecyl phosphite, diphenyl(tridecyl) phosphite, triphenylphosphite, tris(nonylphenyl) phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(2,4-di-t-butyl-5-methylphenyl) phosphite,tris(butoxyethyl) phosphite,4,4′-butylidene-bis(3-methyl-6-t-butylphenyl-tetra-tridecyl)diphosphite, tetra(C12 to C15 mixed alkyl)-4,4′-isopropylidenediphenyldiphosphite, 4,4′-isopropylidenebis(2-t-butylphenyl)-di(nonylphenyl)phosphite, tris(biphenyl) phosphite,tetra(tridecyl)-1,1,3-tris(2-methyl-5-t-butyl-4-hydroxyphenyl)butanediphosphite,tetra(tridecyl)-4,4′-butylidenebis(3-methyl-6-t-butylphenyl)diphosphite, tetra(C1 to C15 mixed alkyl)-4,4′-isopropylidenediphenyldiphosphite, tris(mono-di mixed nonylphenyl) phosphite,4,4′-isopropylidenebis(2-t-butylphenyl)-di(nonylphenyl) phosphite,9,10-di-hydro-9-oxa-10-phosphorphenanthrene-10-oxide,tris(3,5-di-t-butyl-4-hydroxyphenyl) phosphite,hydrogenated-4,4′-isopropylidenediphenyl polyphosphite,bis(octylphenyl)-bis(4,4′-butylidenebis(3-methyl-6-t-butylphenyl)-1,6-hexanoldiphosphite,hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butanetriphosphite, tris(4,4′-isopropylidenebis(2-t-butylphenyl) phosphite,tris(1,3-stearoyloxyisopropyl) phosphite,2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite,2,2-methylenebis(3-methyl-4,6-di-t-butylphenyl)-2-ethylhexyl phosphite,tetrakis(2,4-di-t-butyl-5-methylphenyl)-4,4′-biphenylene diphosphite,and tetrakis(2,4-di-t-butylphenyl)-4,4′-biphenylene diphosphite.

As the phosphite-based stabilizer, one kind may be used, or two or morekinds may be used in combination.

Examples of phosphite-based stabilizers may also includepentaerythritol-type phosphite compounds.

Examples of pentaerythritol-type phosphite compounds include2,6-di-t-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite,2,6-di-t-butyl-4-methylphenyl-methyl-pentaerythritol diphosphite,2,6-di-t-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritol diphosphite,2,6-di-t-butyl-4-methylphenyl-isodecyl-pentaerythritol diphosphite,2,6-di-t-butyl-4-methylphenyl-lauryl-pentaerythritol diphosphite,2,6-di-t-butyl-4-methylphenyl-isotridecyl-pentaerythritol diphosphite,2,6-di-t-butyl-4-methylphenyl-stearyl-pentaerythritol diphosphite,2,6-di-t-butyl-4-methylphenyl-cyclohexyl-pentaerythritol diphosphite,2,6-di-t-butyl-4-methylphenyl-benzyl-pentaerythritol diphosphite,2,6-di-t-butyl-4-methylphenyl-ethylcellosolve-pentaerythritoldiphosphite, 2,6-di-t-butyl-4-methylphenyl-butylcarbitol-pentaerythritoldiphosphite, 2,6-di-t-butyl-4-methylphenyl-octylphenyl-pentaerythritoldiphosphite, 2,6-di-t-butyl-4-methylphenyl-nonylphenyl-pentaerythritoldiphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritoldiphosphite, bis(2,6-di-t-butyl-4-ethylphenyl)pentaerythritoldiphosphite,2,6-di-t-butyl-4-methylphenyl-2,6-di-t-butylphenyl-pentaerythritoldiphosphite,2,6-di-t-butyl-4-methylphenyl-2,4-di-t-butylphenyl-pentaerythritoldiphosphite,2,6-di-t-butyl-4-methylphenyl-2,4-di-t-octylphenyl-pentaerythritoldiphosphite,2,6-di-t-butyl-4-methylphenyl-2-cyclohexylphenyl-pentaerythritoldiphosphite, 2,6-di-t-amyl-4-methylphenyl-phenyl-pentaerythritoldiphosphite, bis(2,6-di-t-amyl-4-methylphenyl)pentaerythritoldiphosphite, and bis(2,6-di-t-octyl-4-methylphenyl)pentaerythritoldiphosphite.

As the pentaerythritol-type phosphate-based stabilizer, one kind may beused, or two or more kinds may be used in combination.

As the pentaerythritol-type phosphite compound,bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite,bis(2,6-di-t-butyl-4-ethylphenyl)pentaerythritol diphosphite,bis(2,6-di-t-amyl-4-methylphenyl)pentaerythritol diphosphite, andbis(2,6-di-t-octyl-4-methylphenyl)pentaerythritol diphosphite arepreferable. Bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritoldiphosphite is more preferable.

Examples of the hindered amine-based stabilizer are not especiallylimited, and may include 4-acetoxy-2,2,6,6-tetramethylpiperidine,4-stearoyloxy-2,2,6,6-tetramethylpiperidine,4-acryloyloxy-2,2,6,6-tetramethylpiperidine,4-(phenylacetoxy)-2,2,6,6-tetramethylpiperidine,4-benzoyloxy-2,2,6,6-tetramethylpiperidine,4-methoxy-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine,4-benzyloxy-2,2,6,6-tetramethylpiperidine,4-phenoxy-2,2,6,6-tetramethylpiperidine,4-(ethylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine,4-(cyclohexylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine,4-(phenylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine,bis(2,2,6,6-tetramethyl-4-piperidyl)-carbonate,bis(2,2,6,6-tetramethyl-4-piperidyl)-oxalate,bis(2,2,6,6-tetramethyl-4-piperidyl)-malonate,bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)-adipate,bis(2,2,6,6-tetramethyl-4-piperidyl)-terephthalate,1,2-bis(2,2,6,6-tetramethyl-4-piperidyloxy)-ethane,α,α′-bis(2,2,6,6-tetramethyl-4-piperidyloxy)-p-xylene,bis(2,2,6,6-tetramethyl-4-piperidyl)-tolylene-2,4-dicarbamate,bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylene-1,6-dicarbamate,tris(2,2,6,6-tetramethyl-4-piperidyl)-benzene-1,3,5-tricarboxylate,tris(2,2,6,6-tetramethyl-4-piperidyl)-benzene-1,3,4-tricarboxylate,1-[2-{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy}butyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]2,2,6,6-tetramethylpiperidine,and a condensation product of 1,2,3,4-butanetetracarboxylic acid,1,2,2,6,6-pentamethyl-4-piperidinol, andβ,β,β′,β′-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)undecane]diethanol.

As the hindered amine-based stabilizer, one kind may be used, or two ormore kinds may be used in combination.

Examples of the triazine-based stabilizers are not especially limited,and may include hydroxyphenyl triazines.

Examples of the hydroxyphenyl triazines include2,4,6-tris(2′-hydroxy-4′-octyloxy-phenyl)-1,3,5-triazine,2-(2′-hydroxy-4′-hexyloxy-phenyl)-4,6-diphenyl-1,3,5-triazine,2-(2′-hydroxy-4′-octyloxyphenyl)-4,6-bis(2′,4-dimethylphenyl)-1,3,5-triazine,2-(2′,4′-dihydroxyphenyl)-4,6-bis(2′,4′-dimethylphenyl)-1,3,5-triazine,2,4-bis(2′-hydroxy-4′-propyloxy-phenyl)-6-(2′,4′-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4′-methylphenyl)-1,3,5-triazine,2-(2′-hydroxy-4′-dodecyloxyphenyl)-4,6-bis(2′,4′-dimethylphenyl)-1,3,5-triazine,2,4,6-tris(2′-hydroxy-4′-isopropyloxyphenyl)-1,3,5-triazine,2,4,6-tris(2′-hydroxy-4′-n-hexyloxyphenyl)-1,3,5-triazine, and2,4,6-tris(2′-hydroxy-4′-ethoxycarbonylmethoxyphenyl)-1,3,5-triazine.

As the triazine-based stabilizer, one kind may be used, or two or morekinds may be used in combination.

Examples of sulfur-based stabilizers are not especially limited, and mayinclude pentaerythrityltetrakis(3-laurylthiopropionate),dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, anddistearyl-3,3′-thiodipropionate.

As the sulfur stabilizer, one kind may be used, or two or more kinds maybe used in combination.

Examples of inorganic phosphorus-based stabilizers are not especiallylimited, and may include phosphoric acids, phosphorous acids,hypophosphorous acids, phosphoric acid metal salts, phosphorous acidmetal salts, and hypophosphorous acid metal salts.

Examples of phosphoric acids, phosphorous acids, and hypophosphorousacids include phosphoric acid, phosphorous acid, hypophosphorous acid,pyrophosphorous acid, and diphosphorous acid.

Examples of the phosphoric acid metal salts, phosphorous acid metalsalts, and hypophosphorous acid metal salts include salts formed fromcompounds of the above-described phosphoric acids and the like withGroup 1 metals in the periodic table.

It is preferred that the inorganic phosphorus-based stabilizer is asoluble compound. Examples thereof include sodium phosphate, sodiumphosphite, and sodium hypophosphite. More preferred is sodium phosphiteand sodium hypophosphite, and still more preferred is sodiumhypophosphite.

The inorganic phosphorus-based stabilizer may also be a hydrate(preferably, a hydrate of sodium hypophosphite (NaH₂PO₂.nH₂O)).

As the inorganic phosphorus-based stabilizer, one kind may be used, ortwo or more kinds may be used in combination.

A blend amount of the (F) stabilizer in the polyamide compositionaccording to the present embodiment is preferably 0.01 to 5 parts bymass, more preferably 0.02 to 1 part by mass, and still more preferably0.1 to 1 part by mass, based on 100 parts by mass of the polyamide.

By blending 0.01 parts by mass or more of the (F) stabilizer a polyamidecomposition which has excellent resistance to heat discoloration andweatherability can be obtained. In addition, by blending 5 parts by massor more of the (F) stabilizer, silver streaks on the surface of themolded product during molding of the polyamide composition can besuppressed, and a molded product having excellent mechanical propertiessuch as toughness and rigidity can be obtained.

A method for producing the polyamide composition comprising the (F)stabilizer according to the present embodiment is not especiallylimited, as long as it is a method which mixes the above-described (A)polyamide and the (F) stabilizer. Examples thereof include blending thestabilizer in the polyamide, blending the stabilizer duringpolymerization of the polyamide, blending the stabilizer when mixing thepolyamide with another resin, adhering the stabilizer to the surface ofa powder or pellet of the polyamide, blending the stabilizer in thepolyamide by melt kneading, and blending a master batch of thestabilizer in the polyamide. Alternatively, a combination of theseblending methods may be employed.

Examples of the method for mixing the polyamide and the stabilizerinclude mixing the polyamide and the stabilizer using a Henschel mixeror the like, then feeding the resultant mixture to a melt kneader andkneading, and blending the stabilizer in a polyamide turned into a meltstate by a single-screw or twin-screw extruder from a side feeder.

The method for feeding the components constituting the polyamidecomposition can be carried out by feeding all of the constituentcomponents all at once to the same feed opening, or by feeding fromdifferent feed openings for each constituent component.

The melt kneading temperature is preferably about 250 to 375° C. at aresin temperature.

The melt kneading time is preferably about 0.5 to 5 minutes.

As the apparatus for performing the melt kneading, it is preferred touse a known apparatus, for example a melt kneader such as a single-screwor twin-screw extruder, a Banbury mixer, and a mixing roll.

To the extent that the object of the present embodiment is not harmed,the polyamide composition comprising the (F) stabilizer may compriseadditives which are customarily used in polyamides, such as an inorganicfiller, a pigment, a dye, a fire retardant, a lubricant, a fluorescentbleaching agent, a plasticizing agent, an organic antioxidant, anultraviolet absorber, nucleating agent, rubber, and a reinforcement.

A relative viscosity ηr at 25° C., a melting point Tm2, and a glasstransition temperature Tg of the polyamide composition comprising the(F) stabilizer according to the present embodiment can be measured bythe same methods as the measurement methods for the above-describedpolyamide. Further, by setting the measurement values for the polyamidecomposition comprising the (F) stabilizer in the same ranges as theranges preferred for the measurement values of the above-describedpolyamide, a polyamide composition having excellent heat resistance,moldability, and chemical resistance can be obtained.

The polyamide composition comprising the (F) stabilizer according to thepresent embodiment preferably has a melt shear viscosity ηs of 20 to 110Pa·s, more preferably 25 to 90 Pa·s, and still more preferably 30 to 80Pa·s.

The melt shear viscosity can be measured based on the method describedin the below examples.

By setting the melt shear viscosity to be in the above-described range,a polyamide composition having excellent fluidity can be obtained.

The polyamide composition preferably has a tensile strength of 80 MPa ormore, more preferably 85 MPa or more, and still more preferably 90 MPaor more.

Measurement of the tensile strength can be carried out based on ASTMD638 as described in the below examples.

By setting the tensile strength to be 80 MPa or more, a polyamidecomposition having excellent rigidity can be obtained.

The polyamide composition preferably has a tensile elongation of 1.0% ormore, more preferably 2.0% or more, and still more preferably 3.0% ormore.

Measurement of the tensile elongation can be carried out based on ASTMD638 as described in the below examples.

By setting the tensile elongation to be 3.0% or more, a polyamidecomposition having excellent toughness can be obtained.

The polyamide composition preferably has a water absorbance of 5.0% orless, more preferably 4.0% or less, and still more preferably 3.0% orless.

Measurement of the water absorbance can be carried out based on themethod described in the below examples.

By setting the water absorbance to be 5.0% or less, a polyamidecomposition having excellent low water absorbance can be obtained.

The polyamide composition comprising the (F) stabilizer according to thepresent embodiment preferably has a change in color tone Δb before andafter reworking of 9 or less, and more preferably 6 or less.

Measurement of the change in color tone Δb can be carried out based onthe method described in the below examples.

By setting the change in color tone Δb to be 9 or less, a polyamidecomposition having excellent resistance to heat discoloration can beobtained.

The polyamide composition comprising the (F) stabilizer preferably has acolor difference ΔE of 9 or less, and more preferably 5 or less.

Measurement of the color difference ΔE can be carried out based on themethod described in the below examples.

By setting the color difference ΔE to be 9 or less, a polyamidecomposition having excellent weatherability can be obtained.

Molding

The polyamide or polyamide composition according to the presentembodiment can be used to obtain various kinds of molded products usingknown molding methods, such as press molding, injection molding,gas-assisted injection molding, welding molding, extrusion, blowmolding, film molding, hollow molding, multilayer molding, and meltspinning.

The polyamide or polyamide composition according to the presentembodiment can be preferably used as a raw material for automobilecomponents. Examples of automobile components include an air intakesystem component, a cooling system component, an interior component, anexterior component, and an electronic component.

Examples of the automobile air intake system component are notespecially limited, and may include an air intake manifold, anintercooler inlet, an exhaust pipe cover, an inner bushing, a bearingretainer, an engine mount, an engine head cover, a resonator, and a slotbody.

Examples of the automobile cooling system component are not especiallylimited, and may include a chain cover, a thermostat housing, an outletpipe, a radiator tank, an alternator, and a delivery pipe.

Examples of an automobile fuel system component are not especiallylimited, and may include a fuel delivery pipe and a gasoline tank case.Examples of the interior system component are not especially limited,and may include an instrument panel, a console box, a glove box, asteering wheel, and a trimming.

Examples of the external component are not especially limited, and mayinclude a molding, a lamp housing, a front grill, a mud guard, a sidebumper, a door mirror stay, and a roof rail.

Examples of the electrical component are not especially limited, and mayinclude a connector, a wire harness connector, a motor component, a lampsocket, an on-board sensor switch, and a combination switch.

A molded product obtained from the polyamide composition according tothe present embodiment, especially from the polyamide compositioncomprising the (C) copper compound and metal halide, has excellent heatresistance, rigidity, toughness, moldability, low water absorbance andthe like. Further, such a molded product also has even better vibrationfatigue resistance, fluidity, and heat aging resistance. Accordingly,this molded product can be preferably used as an automobile air intakesystem component.

The molded product has a strength half-life of preferably 40 days ormore, more preferably 45 days or more, and still more preferably 50 daysor more. Measurement of the strength half-life can be carried out basedon the method described in the below examples.

By setting the strength half-life to be 40 days or more, an automobileair intake system component having excellent heat resistance, especiallyheat aging resistance, can be obtained.

The molded product has a breaking stress of preferably 45 MPa or more,more preferably 50 MPa or more, and still more preferably 55 MPa ormore. Measurement of the breaking stress can be carried out based on themethod described in the below examples.

By setting the breaking stress to be 45 MPa or more, an automobile airintake system component having excellent vibration fatigue resistancecan be obtained.

The molded product preferably has a water absorbance of 5.0% or less,more preferably 4.0% or less, and still more preferably 3.0% or less.Measurement of the water absorbance can be carried out based on themethod described in the below examples.

By setting the water absorbance to be 5.0% or less, an automobile airintake system component having excellent low water absorbance can beobtained.

A molded product obtained from the polyamide composition according tothe present embodiment, especially from the polyamide compositioncomprising the (C) copper compound and metal halide, has excellent heatresistance, rigidity, toughness, moldability, and low water absorbance.Further, such a molded product also has even better LLC resistance.Accordingly, this molded product can be preferably used as an automobilecooling system component.

The molded product has a strength half-life of preferably 40 days ormore, more preferably 45 days or more, and still more preferably 50 daysor more. Measurement of the strength half-life can be carried out basedon the method described in the below examples.

By setting the strength half-life to be 40 days or more, an automobilecooling system component having excellent heat resistance, especiallyheat aging resistance, can be obtained.

The molded product has a tensile strength retention rate after dippingof preferably 60% or more, more preferably 75% or more, and still morepreferably 80% or more. Measurement of the tensile strength afterdipping can be carried out based on the method described in the belowexamples.

By setting the tensile strength retention rate after dipping to be 60%or more, an automobile cooling system component having excellent LLCresistance can be obtained.

The molded product has a water absorbance of preferably 5.0% or less,more preferably 4.0% or less, and still more preferably 3.0% or less.Measurement of the water absorbance can be carried out based on themethod described in the below examples.

By setting the water absorbance to be 5.0% or less, an automobilecooling system component having excellent low water absorbance can beobtained.

The molded product of the polyamide or polyamide composition accordingto the present embodiment can be obtained using commonly known plasticmolding methods, such as press molding, injection molding, gas-assistedinjection molding, welding molding, extrusion, blow molding, filmmolding, hollow molding, multilayer molding, and melt spinning.

The molded product obtained from the polyamide or polyamide compositionaccording to the present embodiment has excellent heat resistance,toughness, moldability, and low water absorbance. Therefore, in additionto automobile uses, the polyamide or polyamide composition according tothe present embodiment can be preferably used, for example, as amaterial for various parts, such as in electric and electronic parts,industrial materials, and daily and household articles. Further, thepolyamide or polyamide composition according to the present embodimentcan be preferably used in extrusion applications.

Examples of the electric and electronic parts are not especiallylimited, and may include a connector, a switch, a relay, a printedwiring board, an electronic component housing, a power point, a noisefilter, a coil bobbin, and a motor end cap.

Examples of the industrial machinery are not especially limited, and mayinclude a gear, a cam, an insulation block, a valve, a power toolcomponent, an agricultural implement component, and an engine cover.

Examples of the daily and household articles are not especially limited,and may include a button, a food container, and office equipment.

Examples of the extrusion applications are not especially limited, andmay include a film, a sheet, a filament, a tube, a rod, and a hollowmolded product.

EXAMPLES

The present embodiment will now be described in more detail using thefollowing examples and comparative examples. However, the presentembodiment is not limited to only these examples.

The raw materials and measurement methods used in the examples andcomparative examples are shown below. In the present embodiment, 1kg/cm² refers to 0.098 MPa.

Raw Materials

The following compounds were used in the examples.

(a) Dicarboxylic acid

(1) 1,4-Cyclohexanedicarboxylic acid (CHDA), trade name 1,4-CHDA HPGrade (trans/cis (molar ratio)=25/75), manufactured by Eastman ChemicalCompany

(2) Terephthalate acid (TPA), trade name Terephthalate acid,manufactured by Wako Pure Chemical Industries, Ltd.

(3) Adipic acid (ADA), trade name Adipic acid, manufactured by Wako PureChemical Industries, Ltd.

(4) Suberic acid (C8DA), trade name Suberic acid, manufactured by WakoPure Chemical Industries, Ltd.

(5) Azelaic acid (C9DA), trade name Azelaic acid, manufactured by WakoPure Chemical Industries, Ltd.

(6) Sebacic acid (C10DA), trade name Sebacic acid, manufactured by WakoPure Chemical Industries, Ltd.

(7) Dodecanedioic acid (C12DA), trade name Dodecanedioic acid,manufactured by Wako Pure Chemical Industries, Ltd.

(8) Tetradecanedioic acid (C14DA), trade name Tetradecanedioic acid,manufactured by Tokyo Chemical Industry Co., Ltd.

(9) Hexadecanedioic acid (C16DA), trade name Hexadecanedioic acid,manufactured by Tokyo Chemical Industry Co., Ltd.

(b) Diamine

(10) 2-Methylpentamethylenediamine (2 MPD), trade name2-Methyl-1,5-diaminopentane, manufactured by Tokyo Chemical IndustryCo., Ltd.

(11) Hexamethylenediamine (HMD), trade name Hexamethylenediamine,manufactured by Wako Pure Chemical Industries, Ltd.

(12) 1,9-Nonamethylenediamine (NMD), trade name 1,9-Nonanediamine,manufactured by Sigma-Aldrich

(13) 2-Methyloctamethylenediamine (2MOD), produced with reference to theproduction method described in Japanese Patent Laid-Open No. 05-17413.

(14) Mixture of 2,2,4-trimethyl-1,6-hexanediamine and2,4,4-trimethyl-1,6-hexanediamine (TMHD), trade nameC,C,C-1,6-hexanediamine, manufactured by Sigma-Aldrich

(B) Inorganic filler

(15) Glass fiber (GF), trade name ECS03T275H, average fiber diameter 10μm φ, cut length 3 mm, manufactured by Nippon Electric Glass Co., Ltd.

(C) Copper compound and metal halide

(16) Copper iodide (CuI), trade name Copper iodide (I), manufactured byWako Pure Chemical Industries, Ltd.

(17) Potassium iodide (KI), trade name Potassium iodide, manufactured byWako Pure Chemical Industries, Ltd.

(18) Ethylene bis-stearylamide, trade name Armowax EBS, manufactured byLion Corporation

(D) Halogen-based flame retardant

(19) Polystyrene bromide, trade name SAYTEX® HP-7010G (bromine contentbased on elemental analysis: 63 mass %), manufactured by AlbemarleCorporation

(E) Phosphinate

(20) Aluminum diethylphosphinate (DEPA1), produced with reference to theproduction method described in Japanese Patent Laid-Open No. 08-73720.

(F) Stabilizer

(F-1) Phenolic-based stabilizer

(21) N,N′-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionamide)], trade name IRGANOX® 1098, manufactured by Ciba Japan

(F-2) Phosphite-based stabilizer

(22) Bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite,trade name ADEKA STAB® PEP-36, manufactured by ADEKA Corporation

(F-3) Hindered amine-based stabilizer

(23) Bis-(2,2,6,6-tetramethyl 4-piperidyl)-sebacate, trade name Sanol®770, manufactured by Ciba Japan

(F-4) Triazine-based stabilizer

(24) 2-(2′-Hydroxy-4′-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine, tradename TINUVIN® 167FF, manufactured by Ciba Japan

(F-5) Inorganic phosphorus-based stabilizer

(25) Sodium hypophosphite, trade name Sodium hypophosphite, manufacturedby Wako Pure Chemical Industries, Ltd.

(G) Flame retardant auxiliary

(26) Diantimony trioxide, trade name Diantimony trioxide, manufacturedby Daiichi F.R.

(27) Zinc borate 2ZnO.3B₂O₃.3.5H₂O, trade name Firebrake® ZB,manufactured by U.S. Borax

(28) Magnesium hydroxide, trade name Kisuma® 5, average particle size:0.8 μm, manufactured by Kyowa Chemical Industry Co., Ltd.

(H) Polymer comprising an α,β-unsaturated dicarboxylic acid anhydride

(29) Copolymer of styrene and maleic anhydride, trade name DYLARK® 332(copolymer of styrene 85 mass % and maleic anhydride 15 mass %),manufactured by NOVA Chemicals

Amount of Polyamide Component Calculation

The mol % of the (a-1) alicyclic dicarboxylic acid was determined bycalculating the (number of moles of the (a-1) alicyclic dicarboxylicacid added as a raw material monomer/number of moles of all the (a)dicarboxylic acid added as a raw material monomer)×100.

The mol % of the (b-1) diamine having the substituent branched from themain chain was determined by calculating the (excluding theadditionally-added portion, number of moles of the (b-1) diamine havingthe substituent branched from the main chain added as a raw materialmonomer/number of moles of all the (b) diamine added as a raw materialmonomer)×100.

Further, the mol % of the (c) lactam and/or aminocarboxylic acid wasdetermined by calculating the (number of moles of the (c) lactam and/oraminocarboxylic acid added as a raw material monomer/number of moles ofall the (a) dicarboxylic acid+number of moles of all the (b)diamine+number of moles of the (c) lactam and/or aminocarboxylic acidadded as raw material monomers)×100.

Measurement Methods

(1) Melting points Tm1, Tm2 (° C.)

Melting points Tm1, Tm2 were measured using the Diamond-DSC,manufactured by PERKIN-ELMER inc., based on JIS-K7121. Measurement wascarried out under conditions of a nitrogen atmosphere, by taking Tm1 (°C.) as the temperature at the endothermic peak (melting peak) whichappeared when the temperature of a specimen of about 10 mg was increasedto 300 to 350° C. depending on the melting point of the sample at a rateof temperature increase of 20° C./min. Tm2 was taken as the temperatureof the maximum peak temperature of the endothermic peaks (melting peaks)which appeared when, after maintaining the temperature in a melt stateat the maximum temperature for 2 minutes, lowering the temperature to30° C. at a rate of temperature decrease of 20° C./min and then aftermaintaining at 30° C. for 2 minutes, similarly increasing thetemperature at a rate of temperature increase of 20° C./min. The totalpeak surface area was taken as the heat of fusion ΔH (J/g). In caseswhere there was a plurality of peaks, areas having a ΔH of 1 J/g or morewere determined to be peaks. If there are two peaks, for example, one ata melting point of 295° C., ΔH=20 J/q, and another one at a meltingpoint of 325° C., ΔH=5 J/g, the melting point was taken to be 325° C.

(2) Glass Transition Temperature Tg (° C.)

The glass transition temperature was measured using the Diamond-DSC,manufactured by PERKIN-ELMER Inc., based on JIS-K7121. Measurement wascarried out under conditions of using liquid nitrogen to rapidly cool amolten sample obtained by melting a specimen with a hot stage (EP80,manufactured by Mettler) to solidify the sample for use as a measurementsample. Using 10 mg of this sample, the temperature was increased to arange of from 30 to 350° C. at a rate of temperature increase of 20°C./min, and the glass transition temperature was measured.

(3) Relative Viscosity ηr at 25° C.

Measurement of the relative viscosity at 25° C. was carried out based onJIS-K6810. More specifically, using 98% sulfuric acid, a 1%concentration solution (ratio of (polyamide 1 g)/(98% sulfuric acid 100mL)) was prepared, and the relative viscosity was measured undertemperature conditions of 25° C.

(4) Melt Shear Viscosity ηs (Pa·s

Fluidity was evaluated in terms of the melt shear viscosity ηs at ashear rate of 1,000 sec⁻¹ under temperature conditions of +20° C. themelting point determined in the above item (1). More specifically, themeasurement method was carried out using the twin capillary rheometerRH7-2 model manufactured by ROSAND (UK). Two orifices were used, whichhad a die diameter of 1.0 mm, a die inlet angle of 180°, and L/D of 16and 0.25.

(5) Tensile Strength (MPa) and Tensile Elongation (%)

Tensile strength (MPa) and tensile elongation (%) were measured based onASTM D638 using a dumbbell injection molding test piece (3 mm thick) forASTM tensile testing. The molding test piece was molded by mounting adumbbell test piece (3 mm thick) die (die temperature=Tg+20° C.) forASTM tensile testing (ASTM D638) on an injection molding machine (PS40E,manufactured by Nissei Plastic Industrial Co., Ltd.), and molding at acylinder temperature of (Tm2+10)° C. to (Tm2+30)° C.

(6) Water Absorbance (%)

The pre-testing mass (mass before water absorbance) of a dumbbellinjection molding test piece (3 mm thick) for ASTM tensile testing wasmeasured in a post-molding dry state (dry as mold). The test piece wasdipped in 80° C. pure water for 24 hours. The test piece was thenremoved from the water, and moisture adhering to the surface was wipedoff. The test piece was then left for 30 minutes under aconstant-temperature constant-humidity (23° C., 50 RH %) atmosphere, andthe post-molding mass (mass after water absorbance) was measured. Theincrease in the mass after water absorbance as compared with the massbefore water absorbance was taken as the water absorbance amount. Theaverage ratio of the water absorbance amount with respect to the massbefore water absorbance for the number of test runs n=3 was taken as thewater absorbance (%).

(7) Copper Concentration, Halogen Concentration, and Molar Ratio ofHalogen and Copper (Halogen/Cu)

The copper concentration was quantified by charging sulfuric acid into aspecimen, adding nitric acid to the resultant mixture while heating todissolve the organic component, maintaining the volume of the solutionconstant with pure water, and quantifying the concentration by ICPemission analysis (high-frequency plasma emission analysis). A Vista-Promanufactured by Seiko Instruments & Electronics Ltd. was used for theICP emission analysis apparatus.

The halogen concentration was quantified by, using iodine as an example,combusting a specimen in a flask purged with high-purity oxygen,trapping the produced gas in an absorbing solution, and quantifying theiodine in the trapped solution using potentiometric titration with a1/100 N silver nitrate solution.

The molar ratio of halogen and copper (halogen/Cu) was calculated usingthe above respective quantified values from the molecular weightsconverted into moles.

(8) Strength Half-Life (Days)

The dumbbell injection molding test piece (3 mm thick) for ASTM tensiletesting described in the above item (5) was heat treated for apredetermined period in a hot-air oven at 200° C., and the tensilestrength was measured based on ASTM-D638. Then, the tensile strengthafter the heat treatment as compared with the tensile strength beforethe heat treatment was calculated as the tensile strength retentionrate. The length of heat treated time at which the tensile strengthretention rate was 50% was taken as the strength half-life.

(9) Breaking Stress (MPa)

The dumbbell injection molding test piece (3 mm thick) for ASTM tensiletesting described in the above item (5) was loaded with a tension loadby a sinusoidal wave of frequency 20 Hz under a 120° C. atmosphere usingthe hydraulic servo fatigue testing machine EHF-50-10-3 manufactured bySaginomiya Seisakusho Co., Ltd., to determine the breaking stress (MPa)at 1,000,000 times.

(10) Color Tone b Value

Dumbbell injection molding test pieces (ASTM dumbbell, 3 mm thick) forASTM tensile testing were obtained by injection molding a polymer pelletwith an injection molding machine under injection molding conditions ofa cylinder temperature of Tm2+30° C., a die temperature of Tg+20° C.,and a molding cycle of 60 seconds. Using the Colorimeter ND-300Amanufactured by Nippon Denshoku Industries Co., Ltd., the initial moldedproduct color tone b value was determined. Measurement was carried outusing 3 dumbbell injection molding test pieces, measuring each piece 3times at a middle section of the widened portion on the opposite gateside, and taking the average value thereof.

(11) Color Tone Difference Δb

Dumbbell injection molding test pieces (ASTM dumbbell, 3 mm thick) forASTM tensile testing were obtained by injection molding a polymer pelletwith an injection molding machine under injection molding conditions ofa cylinder temperature of Tm2+30° C., a die temperature of Tg+20° C.,and a molding cycle of 60 seconds. Using the Colorimeter ND-300Amanufactured by Nippon Denshoku Industries Co., Ltd., the color tone bvalues of the initial molded product and the molded product after 1,000hours were determined. The difference between these values was taken asΔb. Measurement was carried out using 3 dumbbell injection molding testpieces, measuring each piece 3 times at a middle section of the widenedportion on the opposite gate side, and taking the average value thereof.

(12) Color Difference ΔE

The color difference ΔE after 1,000 hours was evaluated for a naturalcolor molded product based on ISO 4892-2 using a dumbbell injectionmolding test pieces (3 mm thick) for ASTM tensile testing. The Ci4000(xenon lamp) manufactured by ATLAS was used as the testing machine.Using the Colorimeter ND-300A manufactured by Nippon Denshoku IndustriesCo., Ltd., the color difference (ΔE) between the initial molded productand the molded product after 1,000 hours was determined. Measurement wascarried out using 3 dumbbell injection molding test pieces, measuringeach piece 3 times at a middle section of the widened portion on theopposite gate side, and taking the average value thereof.

(13) Trans Isomer Ratio

30 to 40 mg of polyamide was dissolved in 1.2 g of hexafluoroisopropanoldeuteride, and the trans isomer ratio was measured by ¹H-NMR. For1,4-cyclohexanedicarboxylic acid, the trans isomer ratio was determinedfrom the ratio of the peak surface area at 1.98 ppm derived from transisomers and the peak surface areas at 1.77 ppm and 1.86 ppm derived fromcis isomers.

(14) Flame Resistance

Flame resistance was measured using the UL94 method (standard specifiedby Underwriters Laboratories Inc., U.S.A.). Molding of the test piece(127 mm long, 12.7 mm wide, and 1/32 inch thick) was carried out bymounting a die (die temperature=Tg+20° C.) of the UL test piece on aninjection molding machine (PS40E, manufactured by Nissei PlasticIndustrial Co., Ltd.), and performing molding at a cylinder temperatureof (Tm2+20)° C. The injection pressure was +2% the full filling pressureduring the molding of the UL test piece.

Flame graduation was based on the UL 94 standard (vertical burningtest). Further, test pieces which failed V-2 were denoted as V-2 out.

(15) Flow Length (cm)

The flow length was determined by molding a 2 mm thick×15 mm wide piecewith a molding machine set to the below conditions, and evaluating basedon the flow length thereof (filled length, cm).

Molding was carried out by mounting a fluidity evaluation (2 mm thick×15mm wide spiral flow path) die (die temperature=Tg+20° C.) on aninjection molding machine (FN3000, manufactured by Nissei PlasticIndustrial Co., Ltd.), and performing molding at a cylinder temperatureof Tm2+20° C., an injection rate at a 20% setting, and an injectionpressure at a 34% setting.

(16) Full Filling Pressure (%)

The full filling pressure (%) during the UL test piece molding describedin the above item (14) was shown.

The full filling pressure was determined by standardizing the injectionrates (99%) and measuring the minimum pressure capable of completelyfilling melted resin into the filling end inside the die, andcalculating the full filling pressure as a percentage of the maximumpressure that the molding machine can apply.

(17) Tensile Strength Retention Rate after Dipping (%)

The dumbbell injection molding test piece (3 mm thick) for ASTM tensiletesting of the above item (5) was dipped for 1,000 hours in a 130° C.aqueous solution of 50% ethylene glycol. After leaving at roomtemperature, the tensile test of the above item (5) was carried out tomeasure tensile strength. The tensile strength retention rate afterdipping was determined as a ratio with respect to the tensile strengthmeasured after the molding.

Example 1

A polyamide polymerization reaction was carried out by “hot meltpolymerization”.

896 g (5.20 mol) of (a) CHDA and 604 g (5.20 mol) of (b) 2 MPD weredissolved in 1,500 g of distilled water to produce an equimolar 50 mass% uniform aqueous solution of the raw material monomers. 15 g (0.13 mol)of 2 MPD was additionally added to this uniform solution.

The obtained aqueous solution was charged into an autoclave having aninternal volume of 5.4 L (manufactured by Nitto Kouatsu Co., Ltd.). Theautoclave was kept warm until the solution temperature (internaltemperature) was 50° C., and then the contents of the autoclave werepurged with nitrogen. Heating was continued from a solution temperatureof about 50° C. until the pressure in the autoclave tank was, in termsof gauge pressure (in the following, pressure in the tank is alwaysexpressed as gauge pressure), about 2.5 kg/cm² (the solution temperaturein this system was about 145° C.). While removing water from the systemto maintain the pressure in the tank at about 2.5 kg/cm², heating wascontinued so that the concentration of the aqueous solution wasconcentrated to about 75% (the solution temperature in this system wasabout 160° C.). Removal of water was stopped, and then heating wascontinued until the pressure in the tank was about 30 kg/cm² (thesolution temperature in this system was about 245° C.) While removingwater from the system to maintain the pressure in the tank at about 30kg/cm², heating was continued until 50° C. below the final temperature.After the solution temperature increased to 50° C. below the finaltemperature (here, 300° C.), while continuing heating, the pressure inthe tank was lowered over about 120 minutes to atmospheric pressure(gauge pressure of 0 kg/cm²).

Subsequently, the heater temperature was adjusted so that the finaltemperature of the resin temperature (solution temperature) would beabout 350° C. With the resin temperature in that state, the tankcontents were kept for 30 minutes under a reduced pressure of 400 Torrby a vacuum apparatus. Then, the pressure was increased with nitrogen,and the resin was formed into a strand from a lower spinneret (nozzle).This strand was water cooled and cut, then discharged in pellet form toobtain a polyamide. Table 4 shows the measurement results ofmeasurements carried out on the obtained polyamide based on theabove-described measurement methods.

Examples 2 to 21

Polyamide polymerization (“hot melt polymerization”) was carried out bythe method described in Example 1, except that the compounds and amountsshown in Table 1 or 2 were used for the (a) dicarboxylic acid, (b)diamine, and (c) lactam and/or aminocarboxylic acid, and that the resinfinal temperature was the temperature shown in Table 4 or 5. Tables 4and 5 show the measurement results of measurements carried out on theobtained polyamides based on the above-described measurement methods.

Comparative Example 1

Polyamide polymerization (“hot melt polymerization”) was carried out bythe method described in Example 1, except that the compounds and amountsshown in Table 3 were used for the (a) dicarboxylic acid, (b) diamine,and (c) lactam and/or aminocarboxylic acid, and that the resin finaltemperature was the temperature shown in Table 6.

In Comparative Example 1, during the polymerization, since the resinsolidified in the autoclave, a strand could not be extracted. Therefore,after cooling, the solidified product was extracted as a lump. This lumpwas ground with a grinder to form roughly pellet-sized objects. Sincefoaming was severe during molding, a molded product could not beobtained.

Comparative Examples 2 to 7

Polyamide polymerization (“hot melt polymerization”) was carried out bythe method described in Example 1, except that the compounds and amountsshown in Table 3 were used for the (a) dicarboxylic acid, (b) diamine,and (c) lactam and/or aminocarboxylic acid, and that the resin finaltemperature was the temperature shown in Table 6. Table 6 shows themeasurement results of measurements carried out on the obtainedpolyamides based on the above-described measurement methods.

TABLE 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6Example 7 Example 8 Example 9 Example 10 (a) Type CHDA CHDA CHDA CHDACHDA CHDA CHDA CHDA CHDA CHDA Dicarboxylic g 896 896 896 896 896 896 730469 719 851 Acid Moles 5.20 5.20 5.20 5.20 5.20 5.20 4.24 2.72 4.18 4.94Type — — — — — — ADA ADA TPA — g — — — — — — 155 398 174 — Moles — — — —— — 1.06 2.72 1.04 — (b) Diamine Type 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD2MPD 2MPD 2MPD g 604 544 484 423 363 302 369 380 364 574 Moles 5.20 4.684.16 3.64 3.12 2.60 3.18 3.27 3.13 4.94 Type — HMD HMD HMD HMD HMD HMDHMD HMD — g — 60 121 181 242 302 246 253 243 — Moles — 0.52 1.04 1.562.08 2.60 2.12 2.18 2.09 — Type 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD2MPD 2MPD g 15 14 12 11 9 8 9 9 9 14 Moles 0.13 0.12 0.10 0.09 0.08 0.070.08 0.08 0.08 0.12 (c) Lactam Type — — — — — — — — — CPL and/or g — — —— — — — — — 75 Aminocarboxylic Moles — — — — — — — — — 0.66 Acid

TABLE 2 Exam- Exam- Example Example Example Example Example ExampleExample Example Example ple 11 ple 12 13 14 15 16 17 18 19 20 21 (a)Type CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDA Dicarboxylicg 730 715 709 702 689 676 664 518 484 518 469 Acid Moles 4.24 4.16 4.124.08 4.00 3.93 3.86 3.01 2.81 3.01 2.72 Type ADA C8DA C9DA C10DA C12DAC14DA C16DA ADA ADA ADA ADA g 155 181 194 206 230 254 276 293 274 293398 Moles 1.06 1.04 1.03 1.02 1.00 0.98 0.96 2.01 1.87 2.01 2.72 (b)Diamine Type 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD 2MOD 2MOD TMHD 2MPD g616 604 598 592 581 570 560 397 371 397 316 Moles 5.30 5.19 5.14 5.105.00 4.91 4.82 2.51 2.34 2.51 2.72 Type — — — — — — — HMD NMD HMD HMD g— — — — — — — 291 371 291 316 Moles — — — — — — — 2.51 2.34 2.51 2.72Type 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD — — 2MPD g 15 15 15 15 15 14 14— — — 8 Moles 0.13 0.13 0.13 0.13 0.12 0.12 0.12 — — — 0.07 (c) LactamType — — — — — — — — — — — and/or g — — — — — — — — — — — Amino- Moles —— — — — — — — — — — carboxylic Acid

TABLE 3 Comparative Comparative Comparative Comparative ComparativeComparative Comparative Example 1 Example 2 Example 3 Example 4 Example5 Example 6 Example 7 (a) Type CHDA CHDA CHDA — TPA CHDA — Dicarboxylicg 896 379 287 — 689 320 — Acid Moles 5.20 2.20 1.67 — 4.00 1.86 — Type —ADA ADA TPA C12DA C12DA ADA g — 482 568 883 230 641 836 Moles — 3.303.89 5.31 1.00 2.78 5.72 (b) Diamine Type 2MPD 2MPD — 2MPD 2MPD 2MPD — g242 383 −3 370 581 539 — Moles 2.08 3.30 — 3.19 5.00 4.64 — Type HMD HMDHMD HMD — — HMD g 363 256 645 247 — — 664 Moles 3.12 2.20 5.55 2.13 — —5.72 Type 2MPD 2MPD — 2MPD 2MPD 2MPD — g 6 10 — 9 15 13 — Moles 0.050.08 — 0.08 0.12 0.12 — (c) Lactam Type — — — — — — — and/or g — — — — —— — Aminocarboxylic Moles — — — — — — — Acid

TABLE 4 Exam- Exam- Exam- Example 1 Example 2 Example 3 Example 4Example 5 Example 6 Example 7 ple 8 ple 9 ple 10 (a) Dicarboxylic AcidType CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDA Mol % in (a) 100100 100 100 100 100 80 50 80 100 Type — — — — — — ADA ADA TPA — Mol % in(a) — — — — — — 20 50 20 — (b) Diamine Type 2MPD 2MPD 2MPD 2MPD 2MPD2MPD 2MPD 2MPD 2MPD 2MPD Mol % in (b) 100 90 80 70 60 50 60 60 60 100Type — HMD HMD HMD HMD HMD HMD HMD HMD — Mol % in (b) — 10 20 30 40 5040 40 40 — Mol % of [(a) + (b)] in 100 100 100 100 100 100 100 100 10093.7 [(a) + (b) + (c)] (c) Lactam and/or Type — — — — — — — — — CPLAminocarboxylic Acid Mol % of (c) in [(a) + (b) + (c)] — — — — — — — — —6.3 Final Temperature of ° C. 350 350 350 350 340 350 320 300 330 330Resin Temperature Melting Point Tm2 ° C. 327 325 323 327 319 330 290 275308 306 Trans isomer ratio % 70 71 70 70 70 71 70 70 70 68 GlassTransition ° C. 143 149 150 146 146 145 120 100 142 143 Temperature TgRelative Viscosity ηr 2.1 1.9 1.9 2.0 2.0 2.0 2.2 2.2 2.0 1.9 at 25° C.Melt Shear Pa · s 71 50 55 58 67 73 70 70 85 45 Viscosity ηs TensileStrength MPa 101 95 95 94 93 92 89 92 91 92 Tensile Elongation % 7 7 7 76 8 12 15 4 10 Water Absorption % 2.7 2.9 2.8 2.5 2.6 2.6 4.6 5.0 2.43.5 Color Tone b Value −8 −8 −7 −7 −7 −7 −6 −6 −5 −8

TABLE 5 Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Example ExampleExample ple 11 ple 12 ple 13 ple 14 ple 15 ple 16 ple 17 ple 18 19 20 21(a) Dicarboxylic Acid Type CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDACHDA CHDA Mol % in 80 80 80 80 80 80 80 60 60 60 50 (a) Type ADA C8DAC9DA C10DA C12DA C14DA C16DA ADA ADA ADA ADA Mol % in 20 20 20 20 20 2020 40 40 40 50 (a) (b) Diamine Type 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD2MOD 2MOD TMHD 2MPD Mol % in f 100 100 100 100 100 100 100 50 50 50 50(b) Type — — — — — — — HMD NMD HMD HMD Mol % in — — — — — — — 50 50 5050 (b) Mol % of [(a) + (b)] in 100 100 100 100 100 100 100 100 100 100100 [(a) + (b) + (c)] (c) Lactam and/or Type — — — — — — — — — — —Aminocarboxylic Acid Mol % of (c) in [(a) + (b) + (c)] — — — — — — — — —— — Final Temperature of ° C. 320 320 320 320 330 320 320 320 330 320300 Resin Temperature Melting Point Tm2 ° C. 295 292 290 288 286 279 276275 289 278 270 Trans isomer ratio % 70 71 72 70 72 70 68 70 69 70 71Glass Transition ° C. 125 123 121 120 119 115 110 113 100 102 103Temperature Tg Relative Viscosity ηr 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.1 1.92.0 2.0 at 25° C. Melt Shear Pa · s 76 73 71 66 66 53 50 61 55 63 68Viscosity ηs Tensile Strength MPa 97 96 94 92 91 90 87 91 85 83 93Tensile Elongation % 7 12 15 23 25 27 29 12 6 7 11 Water Absorption %3.5 3.0 3.0 2.9 2.8 2.8 2.6 3.9 2.8 3.7 4.8 Color Tone b Value −8 −7 −8−7 −8 −6 −8 −8 −7 −6 −8

TABLE 6 Comparative Comparative Comparative Comparative ComparativeComparative Comparative Example 1 Example 2 Example 3 Example 4 Example5 Example 6 Example 7 (a) Dicarboxylic Acid Type CHDA CHDA CHDA — TPACHDA — Mol % in (a) 100 40 30 — 80 40 — Type — ADA ADA TPA C12DA C12DAADA Mol % in (a) — 60 70 100 20 60 100 (b) Diamine Type 2MPD 2MPD — 2MPD2MPD 2MPD — Mol % in (b) 40 60 — 60 100 100 — Type HMD HMD HMD HMD — —HMD Mol % in (b) 60 40 100 40 — — 100 Mol % of [(a) + (b)] in [(a) +(b) + (c)] 100 100 100 100 100 100 100 (c) Lactam and/ Type — — — — — —— or Aminocarboxylic Acid Mol % of (c) in [(a) + (b) + (c)] — — — — — —— Final Temperature of Resin ° C. 380 300 320 340 300 290 290Temperature Melting Point Tm2 ° C. 352 268 290 310 278 266 262 Transisomer ratio % 72 70 70 — — 68 — Glass Transition Temperature Tg ° C.145 89 74 135 118 82 55 Relative Viscosity ηr at 25° C. 1.9 2.2 2.0 1.92.0 2.2 2.1 Melt Shear Viscosity ηs Pa · s Not 80 71 150 147 65 70measurable Tensile Strength MPa Molding 90 89 87 87 60 80 TensileElongation % impossible 8 10 2 4 38 25 Water Absorption % 6.2 6.1 2.42.6 2.1 6.5 Color Tone b Value −5 −7 2 1 −7 −8

As is clear from the results of Tables 4 to 6, the polyamides ofExamples 1 to 21, in which a specific (a) and (b) were polymerized, hadespecially excellent properties for all of heat resistance, fluidity,toughness, low water absorbance, and rigidity.

In contrast, in Comparative Example 1, which is a polyamide comprisingless than 50 mol % of 2-methylpentamethylenediamine, the resinsolidified during the copolymerization. Consequently, not only could thepolyamide not be extracted as a strand, but a molded product could notbe obtained.

Further, for the polyamide of Comparative Example 4, which was producedby the method disclosed in Patent Document 1, fluidity was too low, andthe molding properties were insufficient. In addition, toughness wasalso insufficient.

Example 22

A polyamide polymerization reaction was carried out by “hot meltpolymerization/solid phase polymerization”.

The hot melt polymerization was carried out using the same chargedamounts and the same procedures as in Example 1 to obtain a polyamide(polyamide (I)). Table 7 shows the measurement results of measurementscarried out on the obtained polyamide based on the above-describedmeasurement methods. 1,300 g of the obtained polyamide was charged intoa ribbon stirring type heating apparatus for solid phase polymerization(Ribocone, manufactured by Okawara Corporation), and the heatingapparatus was purged with nitrogen at room temperature. While stillflowing nitrogen, heating was carried out for 12 hours so that the resintemperature was 200° C. Subsequently, while still flowing nitrogen, thetemperature was lowered. At about 50° C., the resin was extracted fromthe apparatus still as a pellet to obtain a polyamide (polyamide (II)).Table 7 shows the measurement results of measurements carried out on theobtained polyamide based on the above-described measurement methods.

Compared with polyamide (I), polyamide (II), which had been subjected tosolid phase polymerization, had an increased relative viscosity at 25°C. and an increased tensile elongation. There was no change in the transisomer ratio before and after the solid phase polymerization. Further,the degree of coloration also did not change.

Table 7 also shows the measurement results of measurements carried outon the polyamide of Example 1 obtained by hot melt polymerization basedon the above-described measurement methods.

Example 23

A polyamide polymerization reaction was carried out by “prepolymer/solidphase polymerization”.

500 g of distilled water was charged into 896 g (5.20 mol) of (a) CHDAand 604 g (5.20 mol) of (b) 2 MPD to produce an equimolar 33 mass slurryof the raw material monomers. 15 g (0.13 mol) of 2 MPD was additionallyadded to this slurry.

The obtained slurry was charged into an autoclave having an internalvolume of 5.4 L (manufactured by Nitto Kouatsu Co., Ltd.). The contentsof the autoclave were purged with nitrogen. After stirring for 30minutes at the solution temperature of 100° C., the temperature wasincreased over 2 hours to 200° C. At this stage, the pressure in theautoclave tank was 22 kg/cm². The temperature was increased to 220° C.The slurry was kept for 2 hours while removing water from the system tomaintain the pressure in the tank at 22 kg/cm². The pressure in the tankwas then lowered over 60 minutes to atmospheric pressure (gauge pressureof 0 kg/cm²). Subsequently, the resin temperature (solution temperature)was lowered to room temperature, and a flange at a lower portion of theautoclave was removed, whereby a solid-state polyamide prepolymer wasobtained (polyamide (I)). Table 7 shows the measurement results ofmeasurements carried out on the obtained prepolymer based on theabove-described measurement methods. The trans isomer ratio of1,4-cyclohexanedicarboxylic acid of the prepolymer was 85%. Further,coloration was seen for the polyamide (I).

Solid phase polymerization was carried out in the same manner as inExample 22 using 1,300 g of the obtained prepolymer to obtain apolyamide (polyamide (II)). Table 7 shows the measurement results ofmeasurements carried out on the obtained polyamide based on theabove-described measurement methods. Compared with the prepolymer,although the polyamide (II) had an increased relative viscosity,coloration was observed.

Example 24

A polyamide polymerization reaction was carried out by“prepolymer/extrusion polymerization”.

The prepolymer was produced using the same charged amounts and the sameprocedures as in Example 23 to obtain a polyamide prepolymer (polyamide(I)). Using 1,300 g of the obtained prepolymer, post-polymerization wascarried out using an extrusion polymerization apparatus (KRC Kneader,manufactured by Kurimoto, Ltd.) The prepolymer was introduced with ajacket temperature of 350° C. and a degree of vacuum of −0.5 MPa (gaugepressure) so that the dwell time would be 30 minutes. The strand wascooled and cut to obtain a polyamide as a pellet (polyamide (II)). Table7 shows the measurement results of measurements carried out on theobtained polyamide based on the above-described measurement methods.Compared with the prepolymer, although the polyamide (II) had anincreased relative viscosity at 25° C., coloration was observed.

TABLE 7 Example 1 Example 22 Example 23 Example 24 (a) Dicarboxylic AcidType CHDA CHDA CHDA CHDA Mol % in (a) 100 100 100 100 Type — — — — Mol %in (a) — — — — (b) Diamine Type 2MPD 2MPD 2MPD 2MPD Mol % in (b) 100 100100 100 Type — — — — Mol % in (b) — — — — Mol % of [(a) + (b)] in [(a) +(b) + (c)] 100 100 100 100 (c) Lactam and/or Type — — — —Aminocarboxylic Acid Mol % of (c) in [(a) + (b) + (c)] — — — —Polymerization Hot melt Hot melt Prepolymer Prepolymer Conditionspolymerization polymerization Resin Polymerization ° C. 350 350 220 220Temperature (I) Melting Point ° C. — 328 350 350 Tm1 Trans isomer % — 7085 85 ratio Relative — 2.1 1.7 1.7 Viscosity ηr at 25° C. Conditions forIncrease — Solid phase Solid phase Extrusion in Degree of polymerizationpolymerization polymerization Polymerization Temperature for ° C. — 200200 350 Increase in Degree of Polymerization (II) Melting Point ° C. 328329 350 328 Tm1 Trans isomer % 70 71 85 70 ratio Glass Transition ° C.143 147 145 145 Temperature Tg Relative 2.1 2.4 2.3 2.2 Viscosity ηr at25° C. Melt Shear Pa · s 71 121 140 100 Viscosity ηs Tensile StrengthMPa 101 105 100 98 Tensile % 7 15 6 5 Elongation Water Absorption % 2.72.6 2.6 2.7 Color Tone b −8 −8 3 4 Value

Polyamide Composition Comprising (B) Inorganic Filler Example 25

The polyamide of Example 1 was used by drying under a nitrogen flow sothat the moisture content was adjusted to about 0.2 mass %. Using atwin-screw extruder (TEM 35, φL/D=47.6, set temperature 340° C., screwrevolution speed 300 rpm, manufactured by Toshiba Machine Co., Ltd.),this dried polyamide was fed from a top feed opening provided at theuppermost upstream portion of the extruder. Glass fiber (GF) was fedfrom a side feed opening on a downstream side of the extruder (the resinfed from the top feed opening was in a sufficiently molten state). Amelt kneaded product extruded from a die head was cooled in a strandform, which was pelletized to form polyamide composition pellets. Theblend amount was 55 parts by mass of glass fiber (GF) based on 100 partsby mass of polyamide. Table 8 shows the measurement results ofmeasurements carried out on the obtained polyamide composition based onthe above-described measurement methods.

Examples 26 to 45

Examples 26 to 45 were carried out in the same manner as Example 25,except that the respective polyamides of Examples 2 to 21 were usedinstead of the polyamide of Example 1. Tables 8 and 9 show themeasurement results of measurements carried out on the obtainedpolyamide compositions based on the above-described measurement methods.

Example 46

Example 46 was carried out in the same manner as Example 29, except that100 parts by mass of glass fiber (GF) based on 100 parts by mass ofpolyamide was used. Table 9 shows the measurement results ofmeasurements carried out on the obtained polyamide composition based onthe above-described measurement methods.

Comparative Example 8

An attempt was made to carry out Comparative Example 8 in the samemanner as Example 25, except the polyamide of Comparative Example 1 wasused instead of the polyamide of Example 1. However, the extrusion statewas very unstable, and a polyamide composition could not be obtained.

Comparative Examples 9 and 10

Comparative Examples 9 and 10 were carried out in the same manner asExample 25, except that the respective polyamides of ComparativeExamples 2 and 3 were used instead of the polyamide of Example 1. Table10 shows the measurement results of measurements carried out on theobtained polyamide compositions based on the above-described measurementmethods.

Comparative Example 11

Comparative Example 11 was carried out in the same manner as Example 25,except that the polyamide of Comparative Example 4 was used instead ofthe polyamide of Example 1, and 100 parts by mass of glass fiber (GF)based on 100 parts by mass of polyamide was used. Table 10 shows themeasurement results of measurements carried out on the obtainedpolyamide composition based on the above-described measurement methods.

Comparative Examples 12 to 14

Comparative Examples 12 to 14 were carried out in the same manner asExample 25, except that the respective polyamides of ComparativeExamples 5 to 7 were used instead of the polyamide of Example 1. Table10 shows the measurement results of measurements carried out on theobtained polyamide compositions based on the above-described measurementmethods.

TABLE 8 Exam- Exam- Exam- Exam- Exam- Exam- Example Example ExampleExample ple 25 ple 26 ple 27 ple 28 ple 29 ple 30 31 32 33 34 (A) (a)Dicarboxylic Acid Type CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDAMol % in (a) 100 100 100 100 100 100 80 50 80 100 Type — — — — — — ADAADA TPA — Mol % in (a) — — — — — — 20 50 20 — (b) Diamine Type 2MPD 2MPD2MPD 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD Mol % in (b) 100 90 80 70 60 5060 60 60 100 Type — HMD HMD HMD HMD HMD HMD HMD HMD — Mol % in (b) — 1020 30 40 50 40 40 40 — Mol % of [(a) + (b)] in [(a) + (b) + (c)] 100 100100 100 100 100 100 100 100 93.7 (c) Lactam and/or Type — — — — — — — —— CPL Aminocarboxylic Acid Mol % of (c) in [(a) + (b) + (c)] — — — — — —— — — 6.3 Melting Point Tm2 ° C. 327 325 323 327 319 330 290 275 308 306Glass Transition ° C. 143 149 150 146 146 145 120 100 142 143Temperature Tg Relative Viscosity ηr 2.1 1.9 1.9 2.0 2.0 2.0 2.2 2.2 2.01.9 at 25° C. (B) Inorganic Filler Type GF GF GF GF GF GF GF GF GF GFParts by mass 55 55 55 55 55 55 55 55 55 55 based on 100 parts by massof (A) Melt Shear Viscosity ηs Pa · s 108 70 79 84 101 111 106 106 13361 Tensile Strength MPa 216 212 212 211 210 210 208 210 209 210 TensileElongation % 3.1 3.1 3.1 3.1 3.0 3.1 3.2 3.3 3.0 3.2 Water Absorption %1.9 2.1 2.0 1.8 1.6 1.6 3.3 3.5 1.5 2.5

TABLE 9 Example Example Example Example Example Example 35 36 37 38 3940 (A) (a) Dicarboxylic Acid Type CHDA CHDA CHDA CHDA CHDA CHDA Mol % in(a) 80 80 80 80 80 80 Type ADA C8DA C9DA C10DA C12DA C14DA Mol % in (a)20 20 20 20 20 20 (b) Diamine Type 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD Mol %in (b) 100 100 100 100 100 100 Type — — — — — — Mol % in (b) — — — — — —Mol % of [(a) + (b)] in [(a) + (b) + (c)] 100 100 100 100 100 100 (c)Lactam and/or Type — — — — — — Aminocarboxylic Acid Mol % of (c) in[(a) + (b) + (c)] — — — — — — Melting Point Tm2 ° C. 295 292 290 288 286279 Glass Transition ° C. 125 123 121 120 119 115 Temperature TgRelative Viscosity ηr 2.0 2.0 2.0 2.0 2.0 2.0 at 25° C. (B) InorganicFiller Type GF GF GF GF GF GF Parts by mass 55 55 55 55 55 55 based on100 parts by mass of (A) Melt Shear Viscosity ηs Pa · s 117 111 108 9999 75 Tensile Strength MPa 213 212 211 210 209 209 Tensile Elongation %3.1 3.2 3.3 3.5 3.6 3.7 Water Absorption % 2.5 2.1 2.1 2.1 2.0 2.0Example Example Example Example Example Example 41 42 43 44 45 46 (A)(a) Dicarboxylic Acid Type CHDA CHDA CHDA CHDA CHDA CHDA Mol % in (a) 8060 60 60 50 100 Type C16DA ADA ADA ADA ADA — Mol % in (a) 20 40 40 40 50— (b) Diamine Type 2MPD 2MOD 2MOD TMHD 2MPD 2MPD Mol % in (b) 100 50 5050 50 60 Type — HMD NMD HMD HMD HMD Mol % in (b) — 50 50 50 50 40 Mol %of [(a) + (b)] in [(a) + (b) + (c)] 100 100 100 100 100 100 (c) Lactamand/or Type — — — — — — Aminocarboxylic Acid Mol % of (c) in [(a) +(b) + (c)] — — — — — — Melting Point Tm2 ° C. 276 275 289 278 270 319Glass Transition ° C. 110 113 100 102 103 146 Temperature Tg RelativeViscosity ηr 2.0 2.1 1.9 2.0 2.0 2.0 at 25° C. (B) Inorganic Filler TypeGF GF GF GF GF GF Parts by mass 55 55 55 55 55 100 based on 100 parts bymass of (A) Melt Shear Viscosity ηs Pa·s 70 90 79 93 102 134 TensileStrength MPa 207 209 205 204 210 210 Tensile Elongation % 3.7 3.2 3.03.1 3.2 2.0 Water Absorption % 1.8 2.8 2.0 2.6 3.4 1.3

TABLE 10 Comparative Comparative Comparative Comparative ComparativeComparative Comparative Example 8 Example 9 Example 10 Example 11Example 12 Example 13 Example 14 (A) (a) Dicarboxylic Type CHDA CHDACHDA — TPA CHDA — Acid Mol % in (a) 100 40 30 — 80 40 — Type — ADA ADATPA C12DA C12DA ADA Mol % in (a) — 60 70 100 20 60 100 (b) Diamine Type2MPD 2MPD — 2MPD 2MPD 2MPD — Mol % in (b) 40 60 — 60 100 100 — Type HMDHMD HMD HMD — — HMD Mol % in (b) 60 40 100 40 — — 100 Mol % of [(a) +(b)] in [(a) + (b) + (c)] 100 100 100 100 100 100 100 (c) Lactam and/orType — — — — — — — Aminocarboxylic Acid Mol % of (c) in [(a) + (b) +(c)] — — — — — — — Melting Point Tm2 ° C. 352 268 290 310 278 266 262Glass Transition ° C. 145 89 74 135 118 82 55 Temperature Tg RelativeViscosity 1.9 2.2 2.0 1.9 2.0 2.2 2.1 ηr at 25° C. (B) Inorganic FillerType GF GF GF GF GF GF GF Parts by mass based 55 55 55 100 55 55 55 on100 parts by mass of (A) Melt Shear Viscosity ηs Pa · s Not measurable124 108 240 205 70 98 Tensile Strength MPa Extrusion 209 208 207 207 189202 Tensile Elongation % impossible 3.1 3.2 1.9 3.0 4.0 3.6 WaterAbsorption % 4.4 4.3 1.4 2.0 1.3 4.6

From the results of Tables 8 to 10, the polyamide compositions ofExamples 25 to 46, which comprise a polyamide obtained by polymerizationof a specific (a) and (b) and an inorganic filler, had especiallyexcellent properties for all of heat resistance, fluidity, toughness,low water absorbance, and rigidity.

In contrast, in Comparative Example 8, which comprises a polyamideobtained by polymerization of less than 50 mol % of2-methylpentamethylenediamine, the extrusion state was unstable, and apolyamide composition could not be obtained.

Further, for the polyamide compositions of Comparative Examples 9 and10, which comprise a polyamide obtained by polymerization of less than50 mol % of an alicyclic dicarboxylic acid, heat resistance and lowwater absorbance were poor.

In addition, for the polyamide composition of Comparative Example 11,which comprises a polyamide produced by the method disclosed in PatentDocument 1, melt shear viscosity was large, fluidity was too low, andthe molding properties were insufficient. In addition, tensileelongation was small and toughness was also insufficient.

Polyamide Composition Comprising (C) Copper Compound and Metal HalideProduction Example 1

A mixture of KI and ethylene bis-stearylamide was obtained by mixing85.1 parts by mass of KI and 10 parts by mass of ethylenebis-stearylamide. The mixture was thoroughly mixed with 4.9 parts bymass of CuI, and the resultant product was granulated with a diskpelleter (F5-11-175, manufactured by Fuji Paudal Co., Ltd.) to obtaingranules (1).

Production Example 2

A mixture of KI and ethylene bis-stearylamide was obtained by mixing80.7 parts by mass of KI and 10 parts by mass of ethylenebis-stearylamide. The mixture was thoroughly mixed with 9.3 parts bymass of CuI, and the resultant product was granulated with a diskpelleter (F5-11-175, manufactured by Fuji Paudal Co., Ltd.) to obtaingranules (2).

Production Example 3

A mixture of KI and ethylene bis-stearylamide was obtained by mixing88.0 parts by mass of KI and 10 parts by mass of ethylenebis-stearylamide. The mixture was thoroughly mixed with 2.0 parts bymass of CuI, and the resultant product was granulated with a diskpelleter (F5-11-175, manufactured by Fuji Paudal Co., Ltd.) to obtaingranules (3).

Example 47

A polyamide composition was obtained by blending 6.1 parts by mass ofthe granules (1) produced in Production Example 1 and 55 parts by massof inorganic filler (GF) based on 100 parts by mass of the polyamide ofExample 1, and melt kneading the resultant mixture with a twin-screwextruder (TEM 35, φL/D=47.6, set temperature 340° C., screw revolutionspeed 300 rpm, manufactured by Toshiba Machine Co., Ltd.). Table 11shows the measurement results of measurements carried out on theobtained polyamide composition based on the above-described measurementmethods.

Examples 48 to 67

Examples 48 to 67 were carried out in the same manner as Example 47,except that the respective polyamides of Examples 2 to 21 were usedinstead of the polyamide of Example 1. Tables 11 and 12 show themeasurement results of measurements carried out on the obtainedpolyamide compositions based on the above-described measurement methods.

Comparative Example 15

An attempt was made to carry out Comparative Example 15 in the samemanner as Example 47, except the polyamide of Comparative Example 1 wasused instead of the polyamide of Example 1. However, the extrusion statewas very unstable, and a polyamide composition could not be obtained.

Comparative Examples 16 to 21

Comparative Examples 16 to 21 were carried out in the same manner asExample 47, except that the respective polyamides of ComparativeExamples 2 to 7 were used instead of the polyamide of Example 1. Table13 shows the measurement results of measurements carried out on theobtained polyamide compositions based on the above-described measurementmethods.

Table 14 shows the measurement results of measurements carried out onthe polyamide of Example 29 based on the above-described measurementmethods.

Example 68

Example 68 was carried out in the same manner as Example 51, except that3.1 parts by mass of the granules (1) of Production Example 1 based on100 parts by mass of the polyamide of Example 5 were used. Table 14shows the measurement results of measurements carried out on theobtained polyamide composition based on the above-described measurementmethods.

Example 69

Example 69 was carried out in the same manner as Example 51, except that9.2 parts by mass of the granules (1) of Production Example 1 based on100 parts by mass of the polyamide of Example 5 were used. Table 14shows the measurement results of measurements carried out on theobtained polyamide composition based on the above-described measurementmethods.

Example 70

Example 70 was carried out in the same manner as Example 51, except that12.2 parts by mass of the granules (1) of Production Example 1 based on100 parts by mass of the polyamide of Example 5 were used. Table 14shows the measurement results of measurements carried out on theobtained polyamide composition based on the above-described measurementmethods.

Example 71

Example 71 was carried out in the same manner as Example 51, except that3.2 parts by mass of the granules (2) of Production Example 2 based on100 parts by mass of the polyamide of Example 5 were used. Table 14shows the measurement results of measurements carried out on theobtained polyamide composition based on the above-described measurementmethods.

Example 72

Example 72 was carried out in the same manner as Example 51, except that15.0 parts by mass of the granules (3) of Production Example 3 based on100 parts by mass of the polyamide of Example 5 were used. Table 14shows the measurement results of measurements carried out on theobtained polyamide composition based on the above-described measurementmethods.

TABLE 11 Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple47 ple 48 ple 49 ple 50 ple 51 ple 52 ple 53 ple 54 ple 55 ple 56 (A)(a) Dicarboxylic Acid Type CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDACHDA Mol % in (a) 100 100 100 100 100 100 80 50 80 100 Type — — — — — —ADA ADA TPA — Mol % in (a) — — — — — — 20 50 20 — (b) Diamine Type 2MPD2MPD 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD Mol % in (b) 100 90 80 7060 50 60 60 60 100 Type — HMD HMD HMD HMD HMD HMD HMD HMD — Mol % in (b)— 10 20 30 40 50 40 40 40 — Mol % of [(a) + (b)] in [(a) + (b) + (c)]100 100 100 100 100 100 100 100 100 93.7 (c) Lactam and/or Type — — — —— — — — — CPL Aminocarboxylic Acid Mol % of (c) in [(a) + (b) + (c)] — —— — — — — — — 6.3 Melting Point Tm2 ° C. 327 325 323 327 319 330 290 275308 306 Glass Transition ° C. 143 149 150 146 146 145 120 100 142 143Temperature Tg Relative Viscosity ηr 2.1 2.0 2.1 2.2 2.2 2.2 2.5 2.5 2.22.0 at 25° C. (B) Inorganic Filler Type GF GF GF GF GF GF GF GF GF GFParts by mass based on 55 55 55 55 55 55 55 55 55 55 100 parts by massof (A) (C) Copper Compound Type CuI CuI CuI CuI CuI CuI CuI CuI CuI CuIParts by mass based on 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30100 parts by mass of (A) Metal Halide Type KI KI KI KI KI KI KI KI KI KIParts by mass based on 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 100 partsby mass of (A) Copper Parts by mass based on 1000 1000 1000 1000 10001000 1000 1000 1000 1000 10⁶ parts by mass of (A) Halogen/Copper Moleratio 20 20 20 20 20 20 20 20 20 20 Melt Shear Viscosity ηs Pa · s 10870 79 84 101 111 106 106 133 61 Tensile Strength MPa 216 212 212 211 210210 208 210 209 210 Tensile Elongation % 3.1 3.1 3.1 3.1 3.0 3.1 3.2 3.33.0 3.2 Water Absorption % 1.9 2.1 2.0 1.8 1.6 1.6 3.3 3.5 1.5 2.5Strength Half-life Days 50 47 49 51 52 50 55 55 50 47 Breaking StressMPa 52 46 51 55 56 51 57 55 53 48 Tensile Strength Retention % 80 80 8085 90 90 70 65 90 80 Rate After Dipping

TABLE 12 Example 57 Example 58 Example 59 Example 60 Example 61 Example62 Example 63 Example 64 Example 65 Example 66 Example 67 (A) (a)Dicarboxylic Acid Type CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDACHDA Mol % in (a) 80 80 80 80 80 80 80 60 60 60 50 Type ADA C8DA C9DAC10DA C12DA C14DA C16DA ADA ADA ADA ADA Mol % in (a) 20 20 20 20 20 2020 40 40 40 50 (b) Diamine Type 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD 2MOD2MOD TMHD 2MPD Mol % in (b) 100 100 100 100 100 100 100 50 50 50 50 Type— — — — — — — HMD HMD HMD HMD Mol % in (b) — — — — — — — 50 50 50 50 Mol% of [(a) + (b)] in [(a) + (b) + (c)] 100 100 100 100 100 100 100 100100 100 100 (c) Lactam and/or Type — — — — — — — — — — — AminocarboxylicAcid Mol % of (c) in [(a) + (b) + (c)] — — — — — — — — — — — MeltingPoint Tm2 ° C. 295 292 290 288 286 279 276 275 289 278 270 GlassTransition ° C. 125 123 121 120 119 115 110 113 100 102 103 TemperatureTg Relative Viscosity ηr 2.1 2.2 2.2 2.2 2.1 2.2 2.2 2.4 2.0 2.2 2.3 at25° C. (B) Inorganic Filler Type GF GF GF GF GF GF GF GF GF GF GF Partsby mass based on 55 55 55 55 55 55 55 55 55 55 55 100 parts by mass of(A) (C) Copper Compound Type CuI CuI CuI CuI CuI CuI CuI CuI CuI CuI CuIParts by mass based on 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.300.30 100 parts by mass of (A) Metal Halide Type KI KI KI KI KI KI KI KIKI KI KI Parts by mass based on 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.25.2 100 parts by mass of (A) Copper Parts by mass based on 1000 10001000 1000 1000 1000 1000 1000 1000 1000 1000 10⁶ parts by mass of (A)Halogen/Copper Mole ratio 20 20 20 20 20 20 20 20 20 20 20 Melt ShearViscosity ηs Pa · s 117 111 108 99 99 75 70 90 79 93 102 TensileStrength MPa 213 212 211 210 209 209 207 209 205 204 210 TensileElongation % 3.1 3.2 3.3 3.5 3.6 3.7 3.7 3.2 3.0 3.1 3.2 WaterAbsorption % 2.5 2.1 2.1 2.1 2.0 2.0 1.8 2.8 2.0 2.6 3.4 StrengthHalf-life Days 48 47 48 49 48 44 41 15 12 9 48 Breaking Stress MPa 49 5250 48 45 43 42 40 42 38 47 Tensile Strength Retention % 75 85 90 90 9090 90 85 90 85 50 Rate After Dipping

TABLE 13 Comparative Comparative Comparative Comparative ComparativeComparative Comparative Example 15 Example 16 Example 17 Example 18Example 19 Example 20 Example 21 (A) (a) Dicarboxylic Type CHDA CHDACHDA — TPA CHDA — Acid Mol % in (a) 100 40 30 — 80 40 — Type — ADA ADATPA C12DA C12DA ADA Mol % in (a) — 60 70 100 20 60 100 (b) Diamine Type2MPD 2MPD — 2MPD 2MPD 2MPD — Mol % in (b) 40 60 — 60 100 100 — Type HMDHMD HMD HMD — — HMD Mol % in (b) 60 40 100 40 — — 100 Mol % of [(a) +(b)] in 100 100 100 100 100 100 100 [(a) + (b) + (c)] (c) Lactam and/orType — — — — — — — Aminocarboxylic Acid Mol % of (c) in [(a) + (b) +(c)] — — — — — — — Melting Point Tm2 ° C. 352 268 290 310 278 266 262Glass Transition ° C. 145 89 74 135 118 82 55 Temperature Tg RelativeViscosity ηr 2.1 2.5 2.3 2.1 2.2 2.5 2.6 at 25° C. (B) Inorganic FillerType GF GF GF GF GF GF GF Parts by mass based 55 55 55 55 55 55 55 on100 parts by mass of (A) (C) Copper Compound Type Extrusion CuI CuI CuICuI CuI CuI Parts by mass based impossible 0.30 0.30 0.30 0.30 0.30 0.30on 100 parts by mass of (A) Metal Halide Type KI KI KI KI KI KI Parts bymass based 5.2 5.2 5.2 5.2 5.2 5.2 on 100 parts by mass of (A) CopperParts by mass based 1000 1000 1000 1000 1000 1000 on 10⁶ parts by massof (A) Halogen/Copper Mole ratio 20 20 20 20 20 20 Melt Shear Viscosityηs Pa · s Not measurable 123 106 228 203 72 100 Tensile Strength MPaExtrusion 209 207 206 204 189 202 Tensile Elongation % impossible 3.23.4 2.9 3.0 4.0 3.8 Water Absorption % 4.3 4.4 1.5 2.1 1.5 4.6 StrengthHalf-life Days 50 50 75 65 49 50 Breaking Stress MPa 50 51 44 43 40 58Tensile Strength % 55 55 90 90 85 50 Retention Rate After Dipping

TABLE 14 Example 29 Example 68 Example 69 Example 70 Example 71 Example72 (A) (a) Dicarboxylic Acid Type CHDA CHDA CHDA CHDA CHDA CHDA Mol % in(a) 100 100 100 100 100 100 Type — — — — — — Mol % in (a) — — — — — —(b) Diamine Type 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD Mol % in (b) 60 60 60 6060 60 Type HMD HMD HMD HMD HMD HMD Mol % in (b) 40 40 40 40 40 40 Mol %of [(a) + (b)] in [(a) + (b) + (c)] 100 100 100 100 100 100 (c) Lactamand/or Type — — — — — — Aminocarboxylic Acid Mol % of (c) in [(a) +(b) + (c)] — — — — — — Melting Point Tm2 ° C. 319 319 319 319 319 319Glass Transition ° C. 146 146 146 146 146 146 Temperature Tg RelativeViscosity ηr at 2.2 2.2 2.2 2.2 2.2 2.2 25° C. (B) Inorganic Filler TypeGF GF GF GF GF GF Parts by mass based on 100 55 55 55 55 55 55 parts bymass of (A) (C) Copper Compound Type — CuI CuI CuI CuI CuI Parts by massbased on 100 — 0.15 0.45 0.60 0.30 0.30 parts by mass of (A) MetalHalide Type — KI KI KI KI KI Parts by mass based on 100 — 2.6 7.8 10.42.6 13.1 parts by mass of (A) Copper Parts by mass based on 10⁶ — 5001500 2000 1000 1000 parts by mass of (A) Halogen/Copper Mole ratio — 2020 20 10 50 Melt Shear Viscosity ηs Pa · s 101 102 101 100 103 101Tensile Strength MPa 210 210 211 214 210 211 Tensile Elongation % 3.03.0 3.2 3.0 2.9 3.0 Water Absorption % 1.6 1.8 1.6 1.7 1.7 1.6 StrengthHalf-life Days 2 27 81 119 50 23 Breaking Stress MPa — 56 56 57 56 55Tensile Strength Retention % — 90 88 89 90 90 Rate After Dipping

From the results of Tables 11 to 14, the polyamide compositions ofExamples 51 to 72, which comprise a polyamide obtained by polymerizationof a specific (a) and (b), and a copper compound and metal halide, hadespecially excellent properties for heat resistance, fluidity,toughness, low water absorbance, and rigidity, as well as for heat agingresistance.

In contrast, in Comparative Example 15, which comprises a polyamidecomprising less than 50 mol % of 2-methylpentamethylenediamine, theextrusion state was unstable, and a polyamide composition could not beobtained.

Further, for the polyamide compositions of Comparative Examples 16 and17, which comprise a polyamide obtained by polymerization of less than50 mol % of an alicyclic dicarboxylic acid, heat resistance and lowwater absorbance were poor.

In addition, for the polyamide composition of Comparative Example 18,which comprises a polyamide produced by the method disclosed in PatentDocument 1, melt shear viscosity was large, fluidity was too low, andthe molding properties were insufficient. In addition, tensileelongation was small and toughness was also insufficient.

Polyamide Composition Comprising (D) Halogen-Based Flame RetardantExample 73

The polyamide of Example 1 was used by drying under a nitrogen flow sothat the moisture content was adjusted to about 0.2 mass %. Using atwin-screw extruder (TEM 35, φL/D=47.6, set temperature 340° C., screwrevolution speed 300 rpm, and output rate 50 kg/hr, manufactured byToshiba Machine Co., Ltd.), a pre-blended mixture of the (A) polyamide,a (D) halogen-based flame retardant, a (G) flame retardant auxiliary,and an (H) polymer comprising an α,β-unsaturated dicarboxylic acidanhydride was fed from a top feed opening provided at the uppermostupstream portion of the extruder. A (B) inorganic filler was fed from aside feed opening on a downstream side of the extruder (the resin fedfrom the top feed opening was in a sufficiently molten state). A meltkneaded product extruded from a die head was cooled in a strand form,which was pelletized to form polyamide composition pellets. The blendamount was, based on 100 parts by mass of the (A) polyamide, 45.0 partsby mass of the (D) halogen-based flame retardant, 7.0 parts by mass ofthe (G) flame retardant auxiliary, 4.0 parts by mass of the (H) polymercomprising an α,β-unsaturated dicarboxylic acid anhydride, and 70.0parts by mass of the (B) inorganic filler. Table 15 shows themeasurement results of measurements carried out on the obtainedpolyamide composition based on the above-described measurement methods.

Examples 74 to 93

Examples 74 to 93 were carried out in the same manner as Example 73,except that the polyamides of Examples 2 to 21 were used instead of thepolyamide of Example 1. Tables 15 and 16 show the measurement results ofmeasurements carried out on the obtained polyamide compositions based onthe above-described measurement methods.

Example 94

Example 94 was carried out in the same manner as Example 77, except thatthe (H) polymer comprising an α,β-unsaturated dicarboxylic acidanhydride was not blended, and that 15.0 parts by mass of the (G) flameretardant auxiliary and 75.0 parts by mass of the (B) inorganic fillerwere used. Table 16 shows the measurement results of measurementscarried out on the obtained polyamide composition based on theabove-described measurement methods.

Example 95

Example 95 was carried out in the same manner as Example 77, except that7.0 parts by mass of magnesium hydroxide as the (G) flame retardantauxiliary was used. Table 16 shows the measurement results ofmeasurements carried out on the obtained polyamide composition based onthe above-described measurement methods.

Comparative Example 22

An attempt was made to carry out Comparative Example 22 in the samemanner as Example 73, except the polyamide of Comparative Example 1 wasused instead of the polyamide of Example 1. However, the extrusion statewas very unstable, and a polyamide composition could not be obtained.

Comparative Examples 23 to 28

Comparative Examples 23 to 28 were carried out in the same manner asExample 73, except that the polyamides of Comparative Examples 2 to 7were used instead of the polyamide of Example 1. Table 17 shows themeasurement results of measurements carried out on the obtainedpolyamide compositions based on the above-described measurement methods.

TABLE 15 Example 73 Example 74 Example 75 Example 76 Example 77 Example78 Example 79 Example 80 Example 81 Example 82 (A) (a) Dicarboxylic AcidType CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDA Mol % in (a) 100100 100 100 100 100 80 50 80 100 Type — — — — — — ADA ADA TPA — Mol % in(a) — — — — — — 20 50 20 — (b) Diamine Type 2MPD 2MPD 2MPD 2MPD 2MPD2MPD 2MPD 2MPD 2MPD 2MPD Mol % in (b) 100 90 80 70 60 50 60 60 60 100Type — HMD HMD HMD HMD HMD HMD HMD HMD — Mol % in (b) — 10 20 30 40 5040 40 40 — Mol % of [(a) + (b)] in [(a) + (b) + (c)] 100 100 100 100 100100 100 100 100 93.7 (c) Lactam and/or Type — — — — — — — — — CPLAminocarboxylic Acid Mol % of (c) in [(a) + (b) + (c)] — — — — — — — — —6.3 Melting Point Tm2 ° C. 327 325 323 327 319 330 290 275 308 306 GlassTransition Temperature Tg ° C. 143 149 150 146 146 145 120 100 142 143Relative Viscosity ηr at 25° C. 2.1 2.0 2.1 2.2 2.2 2.2 2.5 2.5 2.2 2.0Halogen-based Brominated Polystyrene Parts by mass based 45 45 45 45 4545 45 45 45 45 Flame on 100 parts by mass Retardant of (A) (G) FlameRetardant Auxiliary Type Diantimony Diantimony Diantimony DiantimonyDiantimony Diantimony Diantimony Diantimony Diantimony DiantimonyTrioxide Trioxide Trioxide Trioxide Trioxide Trioxide Trioxide TrioxideTrioxide Trioxide Parts by mass based 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.07.0 7.0 on 100 parts by mass of (A) (H) Polymer Copolymer of Styrene andParts by mass based 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 MaleicAnhydride on 100 parts by mass of (A) (B) Inorganic Glass Fiber Parts bymass based 70 70 70 70 70 70 70 70 70 70 Reinforcing on 100 parts bymass Material of (A) Total of (A), (D), and (H) Parts by mass 149 149149 149 149 149 149 149 149 149 Amount of α,β-Unsaturated DicarboxylicParts by mass 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60 AcidAnhydride Amount of α,β-Unsaturated Dicarboxylic Mass % 0.40 0.40 0.400.40 0.40 0.40 0.40 0.40 0.40 0.40 Acid Anhydride Based on Total of (A),(D), and (H) Flow Length cm 21 31 29 27 23 21 22 22 17 34 TensileStrength MPa 210 198 198 196 194 192 186 192 190 192 Tensile Elongation% 3.5 3.5 3.5 3.5 3.3 3.4 3.4 3.3 3.0 3.6 Water Absorption % 1.2 1.3 1.31.1 1.0 1.0 2.0 2.2 1.0 1.6 UL94VB (Class) V-0 V-0 V-0 V-0 V-0 V-0 V-0V-0 V-0 V-0

TABLE 16 Example Example Example Example Example Example Example ExampleExample Example Example Example Example 83 84 85 86 87 88 89 90 91 92 9394 95 (A) (a) Dicarboxylic Type CHDA CHDA CHDA CHDA CHDA CHDA CHDA CHDACHDA CHDA CHDA CHDA CHDA Acid Mol % in (a) 80 80 80 80 80 80 80 60 60 6050 100 100 Type ADA C8DA C9DA C10DA C12DA C14DA C16DA ADA ADA ADA ADA —— Mol % in (a) 20 20 20 20 20 20 20 40 40 40 50 — — (b) Diamine Type2MPD 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD 2MOD 2MOD TMHD 2MPD 2MPD 2MPD Mol %in (b) 100 100 100 100 100 100 100 50 50 50 50 60 60 Type — — — — — — —HMD NMD HMD HMD HMD HMD Mol % in (b) — — — — — — — 50 50 50 50 40 40 Mol% of [(a) + (b)] in [(a) + (b) + (c)] 100 100 100 100 100 100 100 100100 100 100 100 100 (c) Lactam and/or Type — — — — — — — — — — — — —Aminocarboxylic Acid Mol % of (c) in [(a) + (b) + (c)] — — — — — — — — —— — — — Melting Point Tm2 ° C. 295 292 290 288 286 279 276 275 289 278270 319 319 Glass Transition Temperature Tg ° C. 125 123 121 120 119 115110 113 100 102 103 146 146 Relative Viscosity ηr at 25° C. 2.1 2.2 2.22.2 2.1 2.2 2.2 2.4 2.0 2.2 2.3 2.2 2.2 Halogen- Brominated Parts bymass 45 45 45 45 45 45 45 45 45 45 45 45 45 based Flame Polystyrenebased on 100 parts Retardant by mass of (A) (G) Flame RetardantAuxiliary Type Dianti- Dianti- Dianti- Dianti- Dianti- Dianti- Dianti-Dianti- Dianti- Dianti- Dianti- Dianti- Mag- mony mony mony mony monymony mony mony mony mony mony mony nesium Trioxide Trioxide TrioxideTrioxide Trioxide Trioxide Trioxide Trioxide Trioxide Trioxide TrioxideTrioxide hydroxide Parts by mass 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.07.0 15.0 7.0 based on 100 parts by mass of (A) (H) Polymer Copolymer ofParts by mass 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 — 4.0 Styreneand Maleic based on 100 parts Anhydride by mass of (A) (B) Glass FiberParts by mass 70 70 70 70 70 70 70 70 70 70 70 75 70 Inorganic based on100 parts Reinforcing by mass of (A) Material Total of (A), (D), and (H)Parts by mass 149 149 149 149 149 149 149 149 149 149 149 145 149 Amountof α,β-Unsaturated Parts by mass 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.600.60 0.60 0.60 — 0.60 Dicarboxylic Acid Anhydride Amount ofα,β-Unsaturated Mass % 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.400.40 — 0.40 Dicarboxylic Acid Anhydride Based on Total of (A), (D), and(H) Flow Length cm 20 21 21 23 23 30 31 26 29 25 23 25 24 TensileStrength MPa 202 200 196 192 190 188 182 190 178 174 194 175 193 TensileElongation % 3.3 3.4 3.5 3.7 3.8 3.9 3.9 3.4 3.2 3.3 3.4 3.0 3.2 WaterAbsorption % 1.6 1.3 1.3 1.3 1.3 1.3 1.2 1.7 1.3 1.7 2.1 1.0 1.2 UL94VB(Class) V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0

TABLE 17 Compar- Compar- Compar- Compar- Compar- Compar- Compar- ativeative ative ative ative ative ative Example Example Example ExampleExample Example Example 22 23 24 25 26 27 28 (A) (a) Dicarboxylic AcidType CHDA CHDA CHDA — TPA CHDA — Mol % in (a) 100 40 30 — 80 40 — Type —ADA ADA TPA C12DA C12DA ADA Mol % in (a) — 60 70 100 20 60 100 (b)Diamine Type 2MPD 2MPD — 2MPD 2MPD 2MPD — Mol % in (b) 40 60 — 60 100100 — Type HMD HMD HMD HMD — — HMD Mol % in (b) 60 40 100 40 — — 100 Mol% of [(a) + (b)] in [(a) + (b) + (c)] 100 100 100 100 100 100 100 (c)Lactam and/or Type — — — — — — — Aminocarboxylic Acid Mol % of (c) in[(a) + (b) + (c)] — — — — — — — Melting Point Tm2 ° C. 352 268 290 310278 266 262 Glass Transition Temperature Tg ° C. 145 89 74 135 118 82 55Relative Viscosity ηr at 25° C. 2.1 2.5 2.3 2.1 2.2 2.5 2.6Halogen-based Brominated Polystyrene Parts by mass 45 45 45 45 45 45 45Flame Retardant based on 100 parts by mass of (A) (G) Flame RetardantAuxiliary Type Dianti- Dianti- Dianti- Dianti- Dianti- Dianti- Dianti-mony mony mony mony mony mony mony Trioxide Trioxide Trioxide TrioxideTrioxide Trioxide Trioxide Parts by mass 7.0 7.0 7.0 7.0 7.0 7.0 7.0based on 100 parts by mass of (A) (H) Polymer Copolymer of Styrene andParts by mass 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Maleic Anhydride based on 100parts by mass of (A) (B) Inorganic Glass Fiber Parts by mass 70 70 70 7070 70 70 Reinforcing based on 100 Material parts by mass of (A) Total of(A), (D), and (H) Parts by mass 149 149 149 149 149 149 149 Amount ofα,β-Unsaturated Dicarboxylic Acid Parts by mass 0.60 0.60 0.60 0.60 0.600.60 0.60 Anhydride Amount of α,β-Unsaturated Dicarboxylic Acid Mass %0.40 0.40 0.40 0.40 0.40 0.40 0.40 Anhydride Based on Total of (A), (D),and (H) Flow Length cm Not 18 21 14 14 31 31 measurable Tensile StrengthMPa Extrusion 188 186 182 182 128 168 Tensile Elongation % impossible3.3 3.4 2.7 2.9 4.2 3.8 Water Absorption % 2.7 2.7 1.2 1.4 0.8 3.5UL94VB (Class) V-0 V-0 V-0 V-0 V-0 V-0

From the results of Tables 15 to 17, the polyamide compositions ofExamples 73 to 94, which comprise a polyamide obtained by polymerizationof a specific (a) and (b) and a halogen-based flame retardant, hadespecially excellent properties for all of heat resistance, fluidity,toughness, low water absorbance, and rigidity, as well as excellentflame resistance.

In contrast, in Comparative Example 22, which comprises a polyamideobtained by polymerization of less than 50 mol % of2-methylpentamethylenediamine, the extrusion state was unstable, and apolyamide composition could not be obtained.

Further, for the polyamide compositions of Comparative Examples 23 and24, which comprise a polyamide obtained by polymerization of less than50 mol % of an alicyclic dicarboxylic acid, heat resistance and lowwater absorbance were poor.

In addition, for the polyamide composition of Comparative Example 25,which comprises a polyamide produced by the method disclosed in PatentDocument 1, the flow length was short, fluidity was too low, and themolding properties were insufficient. In addition, tensile elongationwas small and toughness was also insufficient.

For Comparative Example 28, which comprises PA66, heat resistance andlow water absorbance were poor.

Polyamide Composition Comprising (E) Phosphinate and/or DiphosphinateExample 96

The polyamide of Example 1 was used by drying under a nitrogen flow sothat the moisture content was adjusted to about 0.2 mass %. Using atwin-screw extruder having one feed opening (top feed) on the upstreamside and another two feed openings, at a middle section of the extruderand at the downstream side near the die (TEM 35, φL/D=47.6, settemperature 340° C., screw revolution speed 100 rpm, and output rate 30kg/hr, manufactured by Toshiba Machine Co., Ltd.), the (A) polyamide wasfed from the top feed opening provided at the uppermost upstream portionof the extruder, an (E) phosphinate and a (G) flame retardant auxiliarywere fed from the feed opening at the middle section of the extruder,and a (B) inorganic filler was fed from the feed opening on thedownstream side near the die. A melt kneaded product extruded from a diehead was cooled in a strand form, which was pelletized to form polyamidecomposition pellets. The blend amount was, based on 100 parts by mass ofthe (A) polyamide, 42.0 parts by mass of the (E) phosphinate, 2.0 partsby mass of the (G) flame retardant auxiliary, and 48.0 parts by mass ofthe (B) inorganic filler. Table 18 shows the measurement results ofmeasurements carried out on the obtained polyamide composition based onthe above-described measurement methods.

Examples 97 to 116

Examples 97 to 116 were carried out in the same manner as Example 96,except that the polyamides of Examples 2 to 21 were used instead of thepolyamide of Example 1. Tables 18 and 19 show the measurement results ofmeasurements carried out on the obtained polyamide compositions based onthe above-described measurement methods.

Example 117

Example 117 was carried out in the same manner as Example 100, exceptthat the (G) flame retardant auxiliary was not blended. Table 19 showsthe measurement results of measurements carried out on the obtainedpolyamide composition based on the above-described measurement methods.

Example 118

Example 118 was carried out in the same manner as Example 100, exceptthat 2.0 parts by mass of magnesium hydroxide as the (G) flame retardantauxiliary was used. Table 19 shows the measurement results ofmeasurements carried out on the obtained polyamide composition based onthe above-described measurement methods.

Comparative Example 29

An attempt was made to carry out Comparative Example 29 in the samemanner as Example 96, except the polyamide of Comparative Example 1 wasused instead of the polyamide of Example 1. However, the extrusion statewas very unstable, and a polyamide composition could not be obtained.

Comparative Examples 30 to 35

Comparative Examples 30 to 35 were carried out in the same manner asExample 96, except that the polyamides of Comparative Examples 2 to 7were used instead of the polyamide of Example 1. Table 20 shows themeasurement results of measurements carried out on the obtainedpolyamide compositions based on the above-described measurement methods.

TABLE 18 Example 96 Example 97 Example 98 Example 99 Example 100 (A) (a)Dicarboxylic Acid Type CHDA CHDA CHDA CHDA CHDA Mol % in (a) 100 100 100100 100 Type — — — — — Mol % in (a) — — — — — (b) Diamine Type 2MPD 2MPD2MPD 2MPD 2MPD Mol % in (b) 100 90 80 70 60 Type — HMD HMD HMD HMD Mol %in (b) — 10 20 30 40 Mol % of [(a) + (b)] in [(a) + (b) + (c)] 100 100100 100 100 (c) Lactam and/or Type — — — — — Aminocarboxylic Acid Mol %of (c) in [(a) + (b) + (c)] — — — — — Melting Point Tm2 ° C. 327 325 323327 319 Glass Transition Temperature Tg ° C. 143 149 150 146 146Relative Viscosity ηr at 25° C. 2.0 2.0 2.1 2.2 2.2 (E) Phosphinate TypeDEPAI DEPAI DEPAI DEPAI DEPAI Parts by mass based on 42 42 42 42 42 100parts by mass of (A) (G) Flame Retardant Auxiliary Type Zinc borate Zincborate Zinc borate Zinc borate Zinc borate Parts by mass based on 2.02.0 2.0 2.0 2.0 100 parts by mass of (A) (B) Inorganic ReinforcingMaterial Type GF GF GF GF GF Parts by mass based on 48 48 48 48 48 100parts by mass of (A) Full Filling Pressure % 20 33 35 37 40 TensileStrength MPa 170 167 167 166 164 Tensile Elongation % 3.0 3.0 3.0 3.02.9 Water Absorption % 1.1 1.5 1.5 1.3 1.2 UL94VB (Class) V-0 V-0 V-0V-0 V-0 Example 101 Example 102 Example 103 Example 104 Example 105 (A)(a) Dicarboxylic Acid Type CHDA CHDA CHDA CHDA CHDA Mol % in (a) 100 8050 80 100 Type — ADA ADA TPA — Mol % in (a) — 20 50 20 — (b) DiamineType 2MPD 2MPD 2MPD 2MPD 2MPD Mol % in (b) 50 60 60 60 100 Type HMD HMDHMD HMD — Mol % in (b) 50 40 40 40 — Mol % of [(a) + (b)] in [(a) +(b) + (c)] 100 100 100 100 93.7 (c) Lactam and/or Type — — — — CPLAminocarboxylic Acid Mol % of (c) in [(a) + (b) + (c)] — — — — 6.3Melting Point Tm2 ° C. 330 290 275 308 306 Glass Transition TemperatureTg ° C. 145 120 100 142 143 Relative Viscosity ηr at 25° C. 2.2 2.5 2.52.2 2.0 (E) Phosphinate Type DEPAI DEPAI DEPAI DEPAI DEPAI Parts by massbased on 42 42 42 42 42 100 parts by mass of (A) (G) Flame RetardantAuxiliary Type Zinc borate Zinc borate Zinc borate Zinc borate Zincborate Parts by mass based on 2.0 2.0 2.0 2.0 2.0 100 parts by mass of(A) (B) Inorganic Reinforcing Material Type GF GF GF GF GF Parts by massbased on 48 48 48 48 48 100 parts by mass of (A) Full Filling Pressure %42 41 41 46 31 Tensile Strength MPa 162 157 162 161 162 TensileElongation % 2.8 2.8 2.9 2.3 3.1 Water Absorption % 1.2 2.4 2.6 1.1 1.8UL94VB (Class) V-0 V-0 V-0 V-0 V-0

TABLE 19 Example Example Example Example Example Example Example 106 107108 109 110 111 112 (A) (a) Dicarboxylic Acid Type CHDA CHDA CHDA CHDACHDA CHDA CHDA Mol % in (a) 80 80 80 80 80 80 80 Type ADA C8DA C9DAC10DA C12DA C14DA C16DA Mol % in (a) 20 20 20 20 20 20 20 (b) DiamineType 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD Mol % in (b) 100 100 100 100 100100 100 Type — — — — — — — Mol % in (b) — — — — — — — Mol % of [(a) +(b)] in [(a) + (b) + (c)] 100 100 100 100 100 100 100 (c) Lactam and/orType — — — — — — — Aminocarboxylic Acid Mol % of (c) in [(a) + (b) +(c)] — — — — — — — Melting Point Tm2 ° C. 295 292 290 288 286 279 276Glass Transition ° C. 125 123 121 120 119 115 110 Temperature TgRelative Viscosity 2.1 2.2 2.2 2.2 2.2 2.2 2.1 ηr at 25° C. (E)Phosphinate Type DEPAI DEPAI DEPAI DEPAI DEPAI DEPAI DEPAI Parts by mass42 42 42 42 42 42 42 based on 100 parts by mass of (A) (G) FlameRetardant Type Zinc borate Zinc borate Zinc borate Zinc borate Zincborate Zinc borate Zinc borate Auxiliary Parts by mass 2.0 2.0 2.0 2.02.0 2.0 2.0 based on 100 parts by mass of (A) (B) Inorganic Type GF GFGF GF GF GF GF Reinforcing Parts by mass 48 48 48 48 48 48 48 Materialbased on 100 parts by mass of (A) Full Filling Pressure % 43 42 42 40 3533 40 Tensile Strength MPa 171 169 166 162 159 154 161 TensileElongation % 2.9 3.0 3.1 3.3 3.5 3.5 3.4 Water Absorption % 1.8 1.6 1.61.5 1.5 1.4 1.5 UL94VB (Class) V-0 V-0 V-0 V-0 V-0 V-0 V-0 ExampleExample Example Example Example Example 113 114 115 116 117 118 (A) (a)Dicarboxylic Acid Type CHDA CHDA CHDA CHDA CHDA CHDA Mol % in (a) 60 6060 50 100 100 Type ADA ADA ADA ADA — — Mol % in (a) 40 40 40 50 — — (b)Diamine Type 2MOD 2MOD TMHD 2MPD 2MPD 2MPD Mol % in (b) 50 50 50 50 60100 Type HMD NMD HMD HMD HMD — Mol % in (b) 50 50 50 50 40 — Mol % of[(a) + (b)] in [(a) + (b) + (c)] 100 100 100 100 100 100 (c) Lactamand/or Type — — — — — — Aminocarboxylic Acid Mol % of (c) in [(a) +(b) + (c)] — — — — — — Melting Point Tm2 ° C. 275 289 278 270 319 327Glass Transition ° C. 113 100 102 103 146 143 Temperature Tg RelativeViscosity 2.4 2.0 2.2 2.3 2.2 2.0 ηr at 25° C. (E) Phosphinate TypeDEPAI DEPAI DEPAI DEPAI DEPAI DEPAI Parts by mass 42 42 42 42 42 42based on 100 parts by mass of (A) (G) Flame Retardant Type Zinc borateZinc borate Zinc borate Zinc borate — Magnesium Auxiliary hydroxideParts by mass 2.0 2.0 2.0 2.0 — 2.0 based on 100 parts by mass of (A)(B) Inorganic Type GF GF GF GF GF GF Reinforcing Parts by mass 48 48 4848 48 48 Material based on 100 parts by mass of (A) Full FillingPressure % 38 35 39 40 38 21 Tensile Strength MPa 161 151 147 164 165126 Tensile Elongation % 3.0 2.8 2.9 3.0 2.9 2.8 Water Absorption % 2.01.5 1.9 2.5 1.2 1.2 UL94VB (Class) V-0 V-0 V-0 V-0 V-0 V-0

TABLE 20 Comparative Comparative Comparative Comparative ComparativeComparative Comparative Example 29 Example 30 Example 31 Example 32Example 33 Example 34 Example 35 (A) (a) Dicarboxylic Acid Type CHDACHDA CHDA — TPA CHDA — Mol % in (a) 100 40 30 — 80 40 — Type — ADA ADATPA C12DA C12DA ADA Mol % in (a) — 60 70 100 20 60 100 (b) Diamine Type2MPD 2MPD — 2MPD 2MPD 2MPD — Mol % in (b) 40 60 — 60 100 100 — Type HMDHMD HMD HMD — — HMD Mol % in (b) 60 40 100 40 — — 100 Mol % of [(a) +(b)] in [(a) + (b) + (c)] 100 100 100 100 100 100 100 (c) Lactam and/orType — — — — — — — Aminocarboxylic Acid Mol % of (c) in [(a) + (b) +(c)] — — — — — — — Melting Point Tm2 ° C. 352 268 290 310 278 266 262Glass Transition ° C. 145 89 74 135 118 82 55 Temperature Tg RelativeViscosity 2.1 2.5 2.3 2.1 2.2 2.5 2.6 ηr at 25° C. (E) Phosphinate TypeDEPAI DEPAI DEPAI DEPAI DEPAI DEPAI DEPAI Parts by mass 42 42 42 42 4242 42 based on 100 parts by mass of (A) (G) Flame Retardant Type Zincborate Zinc borate Zinc borate Zinc borate Zinc borate Zinc borate Zincborate Auxiliary Parts by mass 2.0 2.0 2.0 2.0 2.0 2.0 2.0 based on 100parts by mass of (A) (B) Inorganic Reinforcing Type GF GF GF GF GF GF GFMaterial Parts by mass 48 48 48 48 48 48 48 based on 100 parts by massof (A) Full Filling Pressure % Extrusion 44 42 54 54 33 33 TensileStrength MPa impossible 159 157 154 154 108 142 Tensile Elongation % 2.82.8 2.0 2.3 3.5 3.3 Water Absorption % 3.2 3.1 1.4 1.7 1.5 3.3 UL94VB(Class) V-0 V-0 V-0 V-0 V-0 V-0

From the results of Tables 18 to 20, the polyamide compositions ofExamples 96 to 118, which comprise a polyamide obtained bypolymerization of a specific (a) and (b) and a phosphinate, hadespecially excellent properties for all of heat resistance, fluidity,toughness, low water absorbance, and rigidity, as well as excellentflame resistance.

In contrast, in Comparative Example 29, which comprises a polyamideobtained by polymerization of less than 50 mol % of2-methylpentamethylenediamine, the extrusion state was unstable, and apolyamide composition could not be obtained.

Further, for the polyamide compositions of Comparative Examples 30 and31, which comprise a polyamide obtained by polymerization of less than50 mol % of an alicyclic dicarboxylic acid, heat resistance and lowwater absorbance were poor.

In addition, for the polyamide composition of Comparative Example 32,which comprises a polyamide produced by the method disclosed in PatentDocument 1, the full filling pressure was large, fluidity was too low,and the molding properties were insufficient. In addition, tensileelongation was small and toughness was also insufficient.

For Comparative Example 35, which comprises PA66, heat resistance andlow water absorbance were poor.

Polyamide Composition Comprising (F) Stabilizer Example 119

A polyamide composition was obtained by blending 0.3 parts by mass of astabilizer (21)N,N′-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl propionamide)]based on 100 parts by mass of the polyamide of Example 1, and meltkneading the resultant mixture using a twin-screw extruder (TEM 35,φL/D=47.6, set temperature 340° C., screw revolution speed 300 rpm,manufactured by Toshiba Machine Co., Ltd.). Table 21 shows themeasurement results of measurements carried out on the obtainedpolyamide composition based on the above-described measurement methods.

Examples 120 to 139

Examples 120 to 139 were carried out in the same manner as Example 119,except that the respective polyamides of Examples 2 to 21 were usedinstead of the polyamide of Example 1. Tables 21 and 22 show themeasurement results of measurements carried out on the obtainedpolyamide compositions based on the above-described measurement methods.

Comparative Example 36

An attempt was made to carry out Comparative Example 36 in the samemanner as Example 119, except the polyamide of Comparative Example 1 wasused instead of the polyamide of Example 1. However, the extrusion statewas very unstable, and a polyamide composition could not be obtained.

Comparative Examples 37 to 42

Comparative Examples 37 to 42 were carried out in the same manner asExample 119, except that the respective polyamides of ComparativeExamples 2 to 7 were used instead of the polyamide of Example 1. Table23 shows the measurement results of measurements carried out on theobtained polyamide compositions based on the above-described measurementmethods.

Example 140

Example 140 was carried out in the same manner as Example 123, exceptthat a stabilizer (22) bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritoldiphosphite was used instead of the stabilizer (21)N,N′-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionamide)]. Table 24 shows the measurement results of measurementscarried out on the obtained polyamide composition based on theabove-described measurement methods.

Example 141

Example 141 was carried out in the same manner as Example 123, exceptthat a stabilizer (23) bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate wasused instead of the stabilizer (21)N,N′-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionamide)]. Table 24 shows the measurement results of measurementscarried out on the obtained polyamide composition based on theabove-described measurement methods.

Example 142

Example 142 was carried out in the same manner as Example 123, exceptthat a stabilizer (24)2-(2′-hydroxy-4′-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine was usedinstead of the stabilizer (21)N,N′-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionamide)]. Table 24 shows the measurement results of measurementscarried out on the obtained polyamide composition based on theabove-described measurement methods.

Example 143

Example 140 was carried out in the same manner as Example 123, exceptthat 0.1 parts by mass of a stabilizer (25) sodium hypophosphite wasused instead of the stabilizer (21)N,N′-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionamide)]. Table 24 shows the measurement results of measurementscarried out on the obtained polyamide composition based on theabove-described measurement methods.

Example 144

Example 144 was carried out in the same manner as Example 123, exceptthat 0.5 parts by mass of the stabilizer (21)N,N′-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl propionamide)]was used based on 100 parts by mass of the polyamide of Example 5. Table24 shows the measurement results of measurements carried out on theobtained polyamide composition based on the above-described measurementmethods.

Example 145

Example 145 was carried out in the same manner as Example 123, exceptthat 3.0 parts by mass of the stabilizer (21)N,N′-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl propionamide)]was used based on 100 parts by mass of the polyamide of Example 5. Table24 shows the measurement results of measurements carried out on theobtained polyamide compositions based on the above-described measurementmethods.

Table 24 also shows the measurement results of measurements carried outon the obtained polyamide of Example 5 based on the above-describedmeasurement methods.

Example 146

A polyamide composition was obtained by blending 0.3 parts by mass ofthe stabilizer (21)N,N′-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl propionamide)]and 0.3 parts by mass of the stabilizer (22)bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite based on100 parts by mass of the polyamide of Example 5, and melt kneading theresultant mixture using a twin-screw extruder (TEM 35, φL/D=47.6, settemperature 340° C., screw revolution speed 300 rpm, manufactured byToshiba Machine Co., Ltd.). Table 24 shows the measurement results ofmeasurements carried out on the obtained polyamide composition based onthe above-described measurement methods.

Example 147

A polyamide composition was obtained by blending 0.3 parts by mass ofthe stabilizer (22) bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritoldiphosphite and 0.3 parts by mass of the stabilizer (24)2-(2′-hydroxy-4′-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine based on100 parts by mass of the polyamide of Example 5, and melt kneading theresultant mixture using a twin-screw extruder (TEM 35, φL/D=47.6, settemperature 340° C., screw revolution speed 300 rpm, manufactured byToshiba Machine Co., Ltd.). Table 24 shows the measurement results ofmeasurements carried out on the obtained polyamide composition based onthe above-described measurement methods.

Example 148

A polyamide composition was obtained by blending 0.3 parts by mass ofthe stabilizer (21)N,N′-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionamide)], 0.3 parts by mass of the stabilizer (22)bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, and 0.3parts by mass of the stabilizer (23)bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate based on 100 parts by massof the polyamide of Example 5, and melt kneading the resultant mixtureusing a twin-screw extruder (TEM 35, φL/D=47.6, set temperature 340° C.,screw revolution speed 300 rpm, manufactured by Toshiba Machine Co.,Ltd.). Table 24 shows the measurement results of measurements carriedout on the obtained polyamide composition based on the above-describedmeasurement method.

Example 149

A polyamide composition was obtained by blending 0.3 parts by mass ofthe stabilizer (21)N,N′-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenylpropionamide)], 0.3 parts by mass of the stabilizer (22)bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, and 0.3parts by mass of the stabilizer (24)2-(2′-hydroxy-4′-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine based on100 parts by mass of the polyamide of Example 5, and melt kneading theresultant mixture using a twin-screw extruder (TEM 35, φL/D=47.6, settemperature 340° C., screw revolution speed 300 rpm, manufactured byToshiba Machine Co., Ltd.). Table 24 shows the measurement results ofmeasurements carried out on the obtained polyamide composition based onthe above-described measurement method.

TABLE 21 Example Example Example Example Example 119 120 121 122 123 (A)(a) Dicarboxylic Acid Type CHDA CHDA CHDA CHDA CHDA Mol % in (a) 100 100100 100 100 Type — — — — — Mol % in (a) — — — — — (b) Diamine Type 2MPD2MPD 2MPD 2MPD 2MPD Mol % in (b) 100 90 80 70 60 Type — HMD HMD HMD HMDMol % in (b) — 10 20 30 40 Mol % of [(a) + (b)] in [(a) + (b) + (c)] 100100 100 100 100 (c) Lactam and/or Type — — — — — Aminocarboxylic AcidMol % of (c) in [(a) + (b) + (c)] — — — — — Melting Point Tm2 ° C. 327325 323 327 319 Glass Transition ° C. 143 149 150 146 146 Temperature TgRelative Viscosity 2.1 2.0 2.1 2.2 2.2 ηr at 25° C. (F) Stabilizer TypeStabilizer Stabilizer Stabilizer Stabilizer Stabilizer (21) (21) (21)(21) (21) Parts by mass based 0.3 0.3 0.3 0.3 0.3 on 100 parts by massof (A) Melt Shear Viscosity ηs Pa · s 71 50 55 58 67 Tensile StrengthMPa 101 95 95 94 93 Tensile Elongation % 7 7 7 7 6 Water Absorption %2.7 2.9 2.8 2.5 2.3 Color Tone Change Δb 4 5 5 4 4 Color Difference ΔE 23 2 3 3 Example Example Example Example Example 124 125 126 127 128 (A)(a) Dicarboxylic Acid Type CHDA CHDA CHDA CHDA CHDA Mol % in (a) 100 8050 80 100 Type — ADA ADA TPA — Mol % in (a) — 20 50 20 — (b) DiamineType 2MPD 2MPD 2MPD 2MPD 2MPD Mol % in (b) 50 60 60 60 100 Type HMD HMDHMD HMD — Mol % in (b) 50 40 40 40 — Mol % of [(a) + (b)] in [(a) +(b) + (c)] 100 100 100 100 93.7 (c) Lactam and/or Type — — — — CPLAminocarboxylic Acid Mol % of (c) in [(a) + (b) + (c)] — — — — 6.3Melting Point Tm2 ° C. 330 290 275 308 306 Glass Transition ° C. 145 120100 142 143 Temperature Tg Relative Viscosity 2.2 2.5 2.5 2.2 2.0 ηr at25° C. (F) Stabilizer Type Stabilizer Stabilizer Stabilizer StabilizerStabilizer (21) (21) (21) (21) (21) Parts by mass based 0.3 0.3 0.3 0.30.3 on 100 parts by mass of (A) Melt Shear Viscosity ηs Pa · s 73 70 7085 45 Tensile Strength MPa 92 89 92 91 92 Tensile Elongation % 8 12 15 410 Water Absorption % 2.3 4.6 5.0 2.1 3.5 Color Tone Change Δb 5 5 5 5 5Color Difference ΔE 3 3 3 3 3

TABLE 22 Example Example Example Example Example Example 129 130 131 132133 134 (A) (a) Dicarboxylic Acid Type CHDA CHDA CHDA CHDA CHDA CHDA Mol% in (a) 80 80 80 80 80 80 Type ADA C8DA C9DA C10DA C12DA C14DA Mol % in(a) 20 20 20 20 20 20 (b) Diamine Type 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD Mol% in (b) 100 100 100 100 100 100 Type Mol % in (b) Mol % of [(a) + (b)]in [(a) + (b) + (c)] 100 100 100 100 100 100 (c) Lactam and/or Type — —— — — — Aminocarboxylic Acid Mol % of (c) in [(a) + (b) + (c)] — — — — —— Melting Point Tm2 ° C. 295 292 290 288 286 279 Glass Transition ° C.125 123 121 120 119 115 Temperature Tg Relative Viscosity ηr at 2.1 2.22.2 2.2 2.1 2.2 25° C. (F) Stabilizer Type Stabilizer StabilizerStabilizer Stabilizer Stabilizer Stabilizer (21) (21) (21) (21) (21)(21) Parts by mass 0.3 0.3 0.3 0.3 0.3 0.3 based on 100 parts by mass of(A) Melt Shear Viscosity ηs Pa · s 76 73 71 66 53 50 Tensile StrengthMPa 97 96 94 92 90 87 Tensile Elongation % 7 12 15 23 27 29 WaterAbsorption % 3.5 3.0 3.0 2.9 2.8 2.6 Color Tone Change Δb 5 5 5 4 5 5Color Difference ΔE 3 3 3 3 3 3 Example Example Example Example Example135 136 137 138 139 (A) (a) Dicarboxylic Acid Type CHDA CHDA CHDA CHDACHDA Mol % in (a) 80 60 60 60 50 Type C16DA ADA ADA ADA ADA Mol % in (a)20 40 40 40 50 (b) Diamine Type 2MPD 2MOD 2MOD TMHD 2MPD Mol % in (b)100 50 50 50 50 Type HMD HMD HMD HMD Mol % in (b) 50 50 50 50 Mol % of[(a) + (b)] in [(a) + (b) + (c)] 100 100 100 100 100 (c) Lactam and/orType — — — — — Aminocarboxylic Acid Mol % of (c) in [(a) + (b) + (c)] —— — — — Melting Point Tm2 ° C. 276 275 289 278 270 Glass Transition ° C.110 113 100 102 103 Temperature Tg Relative Viscosity ηr 2.2 2.4 2.0 2.22.3 at 25° C. (F) Stabilizer Type Stabilizer Stabilizer StabilizerStabilizer Stabilizer (21) (21) (21) (21) (21) Parts by mass 0.3 0.3 0.30.3 0.3 based on 100 parts by mass of (A) Melt Shear Viscosity ηs Pa · s66 61 55 63 68 Tensile Strength MPa 91 91 85 83 93 Tensile Elongation %25 12 6 7 11 Water Absorption % 2.8 3.9 2.8 3.7 4.8 Color Tone Change Δb5 5 4 5 5 Color Difference ΔE 2 2 2 3 3

TABLE 23 Comparative Comparative Comparative Comparative ComparativeComparative Comparative Example 36 Example 37 Example 38 Example 39Example 40 Example 41 Example 42 (A) (a) Dicarboxylic Acid Type CHDACHDA CHDA — TPA CHDA — Mol % in (a) 100 40 30 — 80 40 — Type — ADA ADATPA C12DA C12DA ADA Mol % in (a) — 60 70 100 20 60 100 (b) Diamine Type2MPD 2MPD — 2MPD 2MPD 2MPD — Mol % in (b) 40 60 — 60 100 100 — Type HMDHMD HMD HMD — — HMD Mol % in (b) 60 40 100 40 — — 100 Mol % of [(a) +(b)] in [(a) + (b) + (c)] 100 100 100 100 100 100 100 (c) Lactam and/orType — — — — — — — Aminocarboxylic Acid Mol % of (c) in [(a) + (b) +(c)] — — — — — — — Melting Point Tm2 ° C. 352 268 290 310 278 266 262Glass Transition ° C. 145 89 74 135 118 82 55 Temperature Tg RelativeViscosity ηr at 2.1 2.5 2.3 2.1 2.2 2.5 2.6 25° C. (F) Stabilizer TypeStabilizer Stabilizer Stabilizer Stabilizer Stabilizer StabilizerStabilizer (21) (21) (21) (21) (21) (21) (21) Parts by mass based 0.30.3 0.3 0.3 0.3 0.3 0.3 on 100 parts by mass of (A) Melt Shear Viscosityηs Pa · s Not 81 72 149 146 66 71 measurable Tensile Strength MPaExtrusion 91 90 86 88 62 80 Tensile Elongation % impossible 8 10 2 4 3825 Water Absorption % 6.3 6.1 2.4 2.9 2.2 6.5 Color Tone Change Δb 5 5 55 5 5 Color Difference ΔE 3 3 3 3 3 3

TABLE 24 Example Example Example Example Example Example 5 140 141 142143 144 (A) (a) Dicarboxylic Acid Type CHDA CHDA CHDA CHDA CHDA CHDA Mol% in (a) 100 100 100 100 100 100 Type — — — — — — Mol % in (a) — — — — —— (b) Diamine Type 2MPD 2MPD 2MPD 2MPD 2MPD 2MPD Mol % in (b) 60 60 6060 60 60 Type HMD HMD HMD HMD HMD HMD Mol % in (b) 40 40 40 40 40 40 Mol% of [(a) + (b)] in [(a) + (b) + (c)] 100 100 100 100 100 100 (c) Lactamand/or Type — — — — — — Aminocarboxylic Acid Mol % of (c) in [(a) +(b) + (c)] — — — — — — Melting Point Tm2 ° C. 319 319 319 319 319 319Glass Transition Temperature Tg ° C. 146 146 146 146 146 146 RelativeViscosity ηr at 25° C. 2.2 2.2 2.2 2.2 2.2 2.2 (F) Stabilizer Type —Stabilizer Stabilizer Stabilizer Stabilizer Stabilizer (22) (23) (24)(25) (7) Parts by mass — 0.3 0.3 0.3 0.1 0.5 based on 100 parts by massof (A) Melt Shear Viscosity ηs Pa · s 67 68 65 69 67 66 Tensile StrengthMPa 93 92 93 94 93 93 Tensile Elongation % 6 6 7 6 7 6 Water Absorption% 2.6 2.4 2.3 2.2 2.3 2.3 Color Tone Change Δb 10 5 5 5 5 5 ColorDifference ΔE 11 3 3 3 3 3 Example Example Example Example Example 145146 147 148 149 (A) (a) Dicarboxylic Acid Type CHDA CHDA CHDA CHDA CHDAMol % in (a) 100 100 100 100 100 Type — — — — — Mol % in (a) — — — — —(b) Diamine Type 2MPD 2MPD 2MPD 2MPD 2MPD Mol % in (b) 60 60 60 60 60Type HMD HMD HMD HMD HMD Mol % in (b) 40 40 40 40 40 Mol % of [(a) +(b)] in [(a) + (b) + (c)] 100 100 100 100 100 (c) Lactam and/or Type — —— — — Aminocarboxylic Acid Mol % of (c) in [(a) + (b) + (c)] — — — — —Melting Point Tm2 ° C. 319 319 319 319 319 Glass Transition TemperatureTg ° C. 146 146 146 146 146 Relative Viscosity ηr at 25° C. 2.2 2.2 2.22.2 2.2 (F) Stabilizer Type Stabilizer a) Stabilizer a) Stabilizer a)Stabilizer a) Stabilizer (7) (21) (22) (21) (21) b) Stabilizer b)Stabilizer b) Stabilizer b) Stabilizer (22) (24) (22) (22) c) Stabilizerc) Stabilizer (23) (24) Parts by mass 3.0 a) 0.3 a) 0.3 a) 0.3 a) 0.3based on 100 b) 0.3 b) 0.3 b) 0.3 b) 0.3 parts by mass c) 0.3 c) 0.3 of(A) Melt Shear Viscosity ηs Pa · s 67 68 67 66 67 Tensile Strength MPa94 93 93 94 93 Tensile Elongation % 7 6 7 6 6 Water Absorption % 2.5 2.32.3 2.4 2.3 Color Tone Change Δb 5 4 4 4 4 Color Difference ΔE 2 3 3 2 2

From the results of Tables 21 to 24, the polyamide compositions ofExamples 117 to 149, which comprise a polyamide obtained bypolymerization of a specific (a) dicarboxylic acid and (b) diamine, anda stabilizer, had especially excellent properties for all of heatresistance, fluidity, toughness, low water absorbance, and rigidity, aswell as excellent resistance to heat discoloration and weatherability.

In contrast, in Comparative Example 36, which comprises a polyamideobtained by polymerization of less than 50 mol % of2-methylpentamethylenediamine, the extrusion state was unstable, and apolyamide composition could not be obtained.

Further, for Comparative Examples 37 and 38, which comprise a polyamideobtained by polymerization of less than 50 mol % of an alicyclicdicarboxylic acid, heat resistance and low water absorbance were poor.

In addition, for Comparative Example 39, which comprises a polyamideproduced by the method disclosed in Patent Document 1, the melt shearviscosity was large, fluidity was too low, and the molding propertieswere insufficient. In addition, tensile elongation was small andtoughness was also insufficient.

For Comparative Example 42, which comprises PA66, heat resistance andlow water absorbance were poor.

The present application is based on a Japanese patent application filedon Mar. 12, 2008 (Japanese Patent Application No. 2008-62811), aJapanese patent application filed on Mar. 24, 2008 (Japanese PatentApplication No. 2008-75926), and a Japanese patent application filed onOct. 10, 2008 (Japanese Patent Application No. 2008-264182), whosecontents are hereby incorporated by reference herein.

INDUSTRIAL APPLICABILITY

The present invention can provide a high-melting-point polyamide whichhas excellent heat resistance, fluidity, toughness, low waterabsorbance, and rigidity. Further, the polyamide according to thepresent invention has industrial applicability, and can for example bepreferably used as a molding material for various parts, such as inautomobiles, electric and electronics, industrial materials, and dailyand household articles.

The invention claimed is:
 1. A polyamide obtained by polymerizing (a) adicarboxylic acid component comprising at least 70 mol % of1,4-cyclohexanedicarboxylic acid and at least 0.1 mol % of an aliphaticdicarboxylic acid, and (b) a diamine component comprising at least 50mol % of a diamine having a substituent branched from a main chain,wherein the glass transition temperature of the polyamide is higher than110° C.
 2. The polyamide according to claim 1, wherein the aliphaticdicarboxylic acid has 10 or more carbon atoms.
 3. The polyamideaccording to claim 1, wherein the balance of the dicarboxylic acidcomponent is aromatic dicarboxylic acids.
 4. The polyamide according toclaim 2, wherein the dicarboxylic acid component comprises at least 10mol % of an aliphatic dicarboxylic acid having 10 or more carbon atoms.5. The polyamide according to claim 3, wherein the balance of thedicarboxylic acid component is terephthalic acid.
 6. The polyamideaccording to claim 4, wherein the dicarboxylic acid component comprisesat least 15 mol % of an aliphatic dicarboxylic acid having 10 or morecarbon atoms.